Engineering 
Library 


: 


GAS  AND  FUEL  ANALYSIS 
FOR  ENGINEERS. 


A  COMPEND  FOR  THOSE  INTERESTED  IN  THE 
ECONOMICAL  APPLICATION  OF  FUEL. 


PREPARED  ESPECIALLY  FOR  THE  USE  OF  STUDENTS 

at  the 
MASSACHUSETTS  INSTITUTE  OF  TECHNOLOGY, 


BY 

AUGUSTUS  H.   GILL,   S.B.,  PH.D., 

)N 

Professor  of  Technical  Analysis  at  the 

Massachusetts  Institute  of  Technology,   Boston,   Mass. 

Author  of  "  A  Short  Handbook  of  Oil  Analysis," 

"Engine  Room  Chemistry." 


SEVENTH  EDITION,   REVIjEp^  4AT£>   ENLACED. 
TOTAL    ISSUE,    SEVEN  THOUSAND.     %" 

NEW  YORK 

JOHN   WILEY  &   SONS 
LONDON:   CHAPMAN  &  HALL:   LIMITED 

1913 


&$", 
"7/3 

Engineering 
Library 


Copyright,  1896,  1902,  1907,  1908,  1911,  I9I3, 

BY 
AUGUSTUS  H.  GILL. 


THE   SCIENTIFIC    PRESS 

ROBERT   DRUMMONO   AND   COMPANY 

BROOKLYN,   N.    Y. 


PREFACE. 


THIS  little  book  is  an  attempt  to  present  in  a  con- 
cise yet  clear  form  the  methods  of  gas  and  fuel  analy- 
sis involved  in  testing  the  efficiency  of  a  boiler  plant. 
Its  substance  was  given  originally,  in  the  form  of 
lectures  and  heliotyped  notes,  to  the  students  in  the 
courses  of  Chemical,  Mechanical,  and  Electrical  En- 
gineering, but  in  response  to  requests  it  has  been 
deemed  expedient  to  give  it  a  wider  circulation. 

At  the  time  of  its  conception,  nothing  of  the  kind 
was  known  to  exist  in  the  English  language ;  in 
German  we  now  have  the  excellent  little  book  of  Dr. 
Ferdinand  Fischer,  "  Taschenbuch  fur  Feuerungs- 
Techniker." 

The  present  book  is  the  result  of  six  years'  experi- 
ence in  the  instruction  of  classes  of  about  one  hun- 
dred students.  It  is  in  no  sense  a  copy  of  any  other 
work,  nor  is  it  a  mere  compilation.  The  author  has 
in  every  case  endeavored  to  give  credit  where  any- 
thing has  been  taken  from  outside  sources;  it  is,  how- 

269001  m 


IV  PREFACE, 

ever,  difficult  to    credit    single  ideas,  and    if    he    has 
been  remiss  in  this  respect  it  has  been  unintentional. 

The  study  of  flue-gas  analysis  enables  the  engineer 
to  investigate  the  various  sources  of  loss ;  and  if  this 
compend  stimulates  and  renders  easy  such  investiga- 
tion, the  writer's  purpose  will  have  been  accomplished. 
The  necessary  apparatus  can  be  obtained  from  the 
leading  dealers  in  New  York  City. 

The  author  wishes  to  acknowledge  his  indebtedness 
to  our  former  Professor  of  Analytical  Chemistry,  Dr. 
Thomas  M.  Drown,  and  to  Mrs.  Ellen  H.  Richards, 
by  whose  efforts  the  department  of  Gas  Analysis  was 
established. 

He  will  also    be  grateful  for  any  suggestions  or  cor 
rections  from  the  profession. 

MASSACHUSETTS  INSTITUTE  OF  TECHNOLOGY, 
BOSTON,  November,  1896. 


PREFACE  TO  THE  SIXTH  EDITION. 

THE  changes  made  in  the  present  edition  consist  in 
the  addition  of  Specifications  for  the  Purchase  of  Coal 
and  Fuel  Oil  and  of  the  Sampling  of  Fuel  Oil  and 
Natural  Gas. 

As  in  the  past,  minor  additions  and  corrections  nave 
been  made  where  necessary  to  bring  the  book  up  to 
present  practice. 

MASSACHUSETTS  INSTITUTE  OF  TECHNOLOGY, 
Boston,  November,  1911. 


CONTENTS. 


CHAPTER  I. 

PAGE 

INTRODUCTION.  SAMPLING  —  Sampling-tubes.  SUCTION  APPA- 
RATUS. GAS-HOLDERS i 

CHAPTER  II. 

APPARATUS  FOR  THE  ANALYSIS  or  CHIMNEY-GASES.    Apparatus  of 

Orsat,  Bunte,  and  Elliott II 

CHAPTER  III. 

THE     MEASUREMENT     or     TEMPERATURE.    Thermometers — Lc 

Chatelier  Pyrometer— Metals  and  Salts 25 

CHAPTER  IV. 

CALCULATIONS.  "Pounds  of  Air  per  Pound  of  Coal,"  and  Per- 
centage of  Hsat  Carried  off  by  the  Flue-gases.  Loss  due  to 
Formation  of  Carbonic  Oxide.  Loss  due  to  Unconsumed 
Fuel 28 

CHAPTER  V. 

APPARATUS  FOR  THE  ANALYSIS  OF  FUEL  AND  ILLUMINATING  GASES. 

Apparatus  of  Hempel 36 

CHAPTER  VI. 

PREPARATION  OF  REAGENTS  AND  ARRANGEMENT  OF  THE  LABORA- 
TORY    51 

V 


VI  CONTENTS. 

CHAPTER  VII. 

PAOB 

FUELS,  SOLID,  LIQUID,  AND  GASEOUS:  THEIR  DERIVATION  AND 
COMPOSITION 58 

CHAPTER  VIII. 

FUELS.  METHODS  OF  ANALYSIS  AND  DETERMINATION  or  THE 
HEATING  VALUE.  Determination  of  the  Various  Constituents. 
The  Mahler  Bomb,  the  Parr  Coal-calorimeter,  and  Junkers 
Gas-calorimeter 72 

APPENDIX. 
TABLES 109 

COAL  AND  FUEL  OIL  SPECIFICATIONS 115 


LIST   OF    ILLUSTRATIONS. 


FJO.  PAOK 

1.  GAS  SAMPLING-TUBE 3 

2.  SAMPLING  APPARATUS 4 

3.  SAMPLING  APPARATUS  FOR  MINE-GASES 5 

4.  GAS-TUBE 5 

5.  RICHARDS'S  JET-PUMP 8 

6.  .BUNSEN'S  PUMP 8 

7.  STEAM  AIR-PUMP 9 

8.  ORSAT  GAS  APPARATUS 12 

9.  BUNTE  GAS  APPARATUS 17 

10.  ELLIOTT  GAS  APPARATUS 21 

n.  MELTING-POINT  BOXES 27 

12.  HEMPEL  GAS  APPARATUS 37 

13.  HEMPEL  GAS  APPARATUS 38 

14.  MUENCKE'S  ASPIRATOR 56 

15.  COMBUSTION-FURNACE 74 

16.  MAHLER  BOMB 83 

17.  MAHLER  BOMB  AND  CALORIMETER 84 

18.  PARR'S  CALORIMETER 93 

19.  JUNKERS'  GAS-CALORIMETER,  SECTION 99 

20.  JUNKERS'  GAS-CALORIMETER 100 

vii 


GAS   AND   FUEL  ANALYSIS. 


CHAPTER    I. 
INTRODUCTION   AND   METHODS   OF   SAMPLING. 

UNTIL  within  recent  years,  the  mechanical  engineer 
in  testing  a  boiler  plant  has  been  compelled  to  con- 
tent himself  with  the  bare  statement  of  its  efficiency, 
little  or  no  idea  being  obtained  as  to  the  apportion- 
ment of  the  losses.  Knowing  the  composition  and 
temperature  of  the  chimney-gases  and  the  analysis  of 
the  coal  and  ash,  the  loss  due  to  the  formation  of  car- 
bonic oxide,  to  the  imperfect  combustion  of  the  coal, 
to  the  high  temperature  of  the  escaping  gases,  can 
each  be  determined  and  thus  a  basis  for  their  reduc- 
tion to  a  minimum  established. 

By  the  simple  analysis  of  the  chimney-gases  and 
determination  of  their  temperature,  a  very  good  idea 
of  the  efficiency  of  the  plant  can  be  obtained  previous 
to  making  the  engineering  test.  For  example,  in  a 
test  which  the  author  made  in  connection  with  his 
students,  the  efficiency  was  increased  from  58  to  70 
per  cent,  upon  the  results  of  the  gas  analysis  alone. 


2  GAS   A:\'D    FUEL   ANALYSIS. 

To  this  end  a  representative  sample  must  be  collected 
according  to  the  method  about  to  be  described. 

SAMPLING. 

Before  proceeding  to  take  a  sample  of  the  gas,  the 
plant — for  example,  a  boiler  setting — from  which  the 
gas  is  to  be  taken  should  be  thoroughly  inspected, 
and  all  apertures  by  which  the  air  can  enter,  carefully 
stopped  up.  A  suitable  tube  is  then  inserted  air-tight 
in  the  gas-duct,  connected  with  the  sampling  or  gas 
apparatus,  and  suction  applied,  thus  drawing  the  gas 
out.  Cork,  putty,  plaster  of  Paris,  wet  cotton-waste, 
or  asbestos  may  be  used  to  render  the  joint  gas-tight. 
The  place  of  insertion  should  be  chosen  where  the  gas 
will  be  most  completely  mixed  and  least  contaminated 
with  air.  The  oil-bath  containing  the  thermometer  is 
similarly  inserted  near  the  gas-tube,  and  the  tempera- 
ture read  from  time  to  time. 

I.  Tubes. — The  tubes  usually  employed  are  Bohe- 
mian-glass combustion  tubing  or  water-cooled  metal 
tubes;  those  of  porcelain  or  platinum  are  also  some- 
times used.  Glass  and  porcelain  tubes  when  subjected 
to  high  temperatures  must  be  previously  warmed  or 
gradually  inserted:  the  former  may  be  used  up  to 
temperatures  of  600°  C.  (1200°  F.).  Uncooled  metal 
tubes,  other  than  those  of  platinum,  should  under  no 
circumstances  be  used.* 

*  Fischer,  "Technologic  der  Brennstoffe,"  1880,  p.  221,  states 
that  the  composition  of  a  gaseous  mixture  was  changed  from  1.5 
to  26.0  per  cent  carbon  dioxide,  by  the  passage  through  an  iron 
tube  heated  to  a  dull  red  heat,  the  carbonic  oxide  originally 
present  reducing  the  iron  oxide  with  the  formation  of  carbon 
dioxide. 


TNl^RODUCTION  AND  METHODS  OF  SAMPLING.      3 

The  metal  tube  with  the  water  cooling  is  made  as 
shown  in  Fig.  I,  c  being  a  piece  of  brass  pipe  3 
feet  long,  \\  inches  outside  diameter,  b  the  same 
length,  J  inch  in  diameter,  and  a  \  inch  in  diameter. 
The  water  enters  at  d  and  leaves  at  e.  The  walls  of 


A 


FIG.  r.— GAS-SAMPLING  TUBE. 

the  tubes  are  TV  inch  thick.  The  joint  at  A  should 
be  brazed;  the  others  may  be  soldered. 

Platinum  tubes  from  their  high  cost  and  small  bore 
are  seldom  used ;  they  are  attacked  by  carbon,  cyan- 
ogen, arsenic,  and  metallic  vapors. 

2.  Apparatus  for  the  Collection  of  Samples. — 
A  convenient  sampling  apparatus  is  shown  in  Fig.  2. 
It  may  be  made  from  a  liter  separatory  funnel — in- 
stead of  the  bulb  there  shown — fitted  with  a  rubber 
stopper  carrying  a  tube  passing  to  the  bottom  and  a 
T  tube;  both  of  these,  except  where  sulphur-con- 
taining gases  are  present,  can  advantageously  be 
made  of  T\-inch  lead  pipe.  The  stopper  should  not 
be  fastened  down  with  wire  between  the  tubes  after 
the  manner  of  wiring  effervescent  drinks,  as  this 
draws  the  rubber  away  from  the  tubes  and  occasions 
a  leak.  The  fastening  shown  consists  of  a  brass  plate 
fitting  upon  the  top  of  the  stopper,  provided  with 
screws  and  nuts  which  pass  through  a  wire  around 


4  GAS  AND    FUEL   ANALYSIS. 

the  neck  of  the  separatory.      A  chain  fastened  to  the 
plate  serves  as  a  convenient  method  of  handling  it. 

In  using  the  apparatus,  the  bulb  is  filled  with  water 
by  connecting  the  stem  with  the  water-supply  and 
opening  one  of  the  pinchcocks  upon  the  T  tube;  the 


FIG.  2. — SAMPLING  APPARATUS. 

water  thus  entering  from  the  bottom  forces  the  air 
out  before  it.  One  branch  of  the  T  is  connected  with 
the  sampling-tube  and  the  other  with  the  suction- 
pump,  the  stopcocks  being  open,  and  a  current  of  gas 
drawn  down  into  the  pump;  upon  opening  the  cock 
upon  the  stem,  the  water  runs  out,  drawing  a  small 
portion  of  the  gas-current  passing  through  the  T  after 
it  into  the  bulb.  It  is  then  taken  to  a  convenient 


INTRODUCTION  AND  METHODS  OF  SAMPLING.      5 

place  for  analysis,  the  tube  //  connected  with  a  head  of 
water,  a  branch  of  the  T  z,  with  the  gas  apparatus,  and 
a  sample  of  gas  forced  over  into  the  letter  for  analysis. 


FIG.  4. — GAS-TUBE.      FIG.  3. — SAMPLING  APPARATUS  FOR 

MINE-GASES. 

Enough  water  should  be  left  in  the  bulb  to  seal  the 
stopcock  on  the  bottom  and  prevent  leakage.  This 
apparatus  is  better  adapted  for  the  needs,  of  the  class- 


O  GAS  AND   FUEL   ANALYSIS. 

room  than  for  actual  practice,  as  it  enables  the  same 
sample  to  be  given  to  eight  or  ten  students.  As  has 
been  shown  by  several  years'  experience,  the  water 
exercises  no  appreciable  solvent  action  upon  the 
gaseous  mixture  in  the  time — about  half  an  hour — 
necessary  to  collect  and  distribute  the  samples.  It  is 
often  necessary  to  attach  about  a  yard  of  -^-inch 
rubber  tubing  to  the  stem  of  the  bulb  to  prevent  air 
being  sucked  up  through  it  when  taking  a  sample. 

In  the  actual  boiler-test  it  is  preferable  to  insert  a 
T  instead  of  this  apparatus  in  the  gas-stream,  connect 
the  gas  apparatus  to  the  free  branch  of  this  T,  and 
draw  the  sample.  In  making  connections  with  gas 
apparatus  the  air  in  the  rubber  connectors  should  be 
displaced  with  water  by  means  of  a  medicine- 
dropper. 

In  the  Saxon  coal-mines,  zinc  cans  of  ten  liters 
capacity,  of  the  form  shown  in  Fig.  3,  are  used  by 
Winkler  for  sampling  the  mine-gases;  they  are  carried 
down  filled  with  water  and  this  allowed  to  run  out, 
and  the  gas  thus  obtained  brought  into  the  laboratory 
and  analyzed.  Small  samples  of  gas  may  very  well  be 
taken  in  tubes  of  100  cc.  capacity  like  Fig.  4,  the 
ends  of  which  are  closed  with  rubber  connectors  and 
glass  plugs.  Rubber  bags  are  not  to  be  recommended 
for  the  collection  and  storage  of  gas  for  analysis,  as 
they  permit  of  the  diffusion  of  gases,  notably  hydro- 
gen. 

3.  Apparatus  for  Producing  Suction. — I.  WATER- 
PUMPS — (a)  Jet-pumps,  depending  for  their  action 
upon  a  considerable  head  of  water,  and  (b)  ti.ose 
depending  rather  upon  a  sufficient  fall  of  water. 


INTRODUCTION  AND  METHODS  OF  SAMPLING.      7 

(a)  Jet-pumps. — -The  Richards'  jet  pump  *  is  shown 
in    section    in    Fig.    5    and   much    resembles   a   boiler 
injector;  it  consists  of  a  water-jet  w,  a  constriction  or 
waist  <?,  a  waste-tube'^,  and  a  tube  for  the  inspiration 
of   air.      The   jet   of   water   forms   successive    pistons 
across  a,  drawing  the  air  in  with  it  and  is  broken  up 
into  foam  by  the  zigzag  tube  o. 

This  pump  is  known  in  Germany  as  Muencke's,  and 
in  England  as  Wing's;  Chapman's  pump  is  also  a 
modified  form. 

It  may  be  easily  constructed  in  glass,  the  jets  pass- 
ing through  rubber  stoppers  which  are  wired  down, 
thus  admitting  of  adjustment  to  the  conditions  under 
which  it  has  to  work.f 

(b)  Fall-pumps. — Bunsen's  pump,   Fig.   6,   consists 
of  a  wide  glass  tube  A,  drawn  out  at  the  bottom  for 
connection  with  a  J-inch  lead  pipe  $,  and  at  the  top 
for  connection  with  c,  the  tube  through  which  the  air 
is  drawn ;   this  tube  is  usually   fused  in,   although   it 
may  be  connected   with  rubber;  a  is  a  rubber  tube 
provided  with  screw  cocks  connected  with  the  water- 
supply;  d  is  connected  with  a  mercury  column,  and 
the  vessel   B  serves   for  the   retention   of  any  water 
which  might  be  drawn  back  into  the  apparatus  evac- 
uated. 

The  tube  b  for  the  best  results  should  be  32  feet  in 
length,  equal  to  the  height  of  a  column  of  water  sup- 
ported by  the  atmosphere,  although  for  the  ordinary 
purposes  of  gas-sampling  it  may  be  shorter. 

When  water  is  admitted  through  a  it  fills  b,  acting 

*  Richards,  Am.  Jour,  of  Science  (3),  8,  412;    Trans.  Am.  Inst. 
Min.  Engrs.,  6,  492  (1874). 

f  The  pump  'vill  also  work  well  using  steam. 


8 


GAS  AND    FUEL   ANALYSIS. 


as  a  continually  falling  piston  drawing  the  current  of 
air  through  e  and  its  connections.  These  various 
forms  of  water-pumps  should  give  a  vacuum  repre- 


jrIGi  5. — RICHARDS'  JET-PUMP.       FIG.  6. — BUNSEN'S  PUMP. 

sented  by  the  height  of  the  barometer  less  the  tension 
of  aqueous  vapor  at  the  temperature  at  which  they 
are  used,  or  about  29  inches  of  mercury. 


INTRODUCTION  AND  METHODS  OF  SAMPLING.      9 

II.  STEAM-PUMPS. --Kochinke  describes  the  appa- 
ratus in  use  in  the  Muldner  Hutten  in  Freiberg, 
shown  at  one-fifth  size  in  Fig.  7.  It  consists  of  a 
glass  tube  drawn  down  to  an  opening  6  mm.  in  diam- 


FIG.  7.— STEAM  AIR-PUMP. 

eter;  concentric  with  this,  and  held  in  place  by  the 
washer  a,  is  the  steam-jet  2  mm.  in  diameter,  passing 
through  the  cork  bt  the  cement  c,  and  covering  d.  It 
is  connected  with  the  steam-pipe  at  g  by  webbed 
rubber  tubing/;  the  air  enters  at  e.  This  is  said  to 
give  very  good  results  and  be  economical  in  use  of 
steam. 

In  case  neither  water  nor  steam  be  available, 
recourse  must  be  had  to  the  ordinary  rubber  syringe- 
bulbs,  provided  with  suitable  valves,  obtainable  at  any 
rubber  store,  or  to  a  bottle  aspirator.  This  consists  of 
two  one-gallon  bottles,  provided  with  doubly  perfor- 
ated rubber  stoppers,  carrying  tubes  of  glass  or  lead 
bent  at  right  angles.  In  each  bottle  one  of  these  tubes 
passes  nearly  to  the  bottom,  and  these  are  connected 
together  by  a  piece  of  rubber  tubing  a  yard  long, 
carrying  a  screw  pinchcock.  The  other  tube  in  each 
case  stops  immediately  under  the  stopper.  Upon 
rilling  one  of  the  bottles  with  water,  inserting  the 
stopper  and  blowing  strongly  through  the  short  tube, 
water  will  fill  the  long  tubes  thus  forming  a  siphon, 


IO  GAS  AND   FUEL   ANALYSIS. 

and  upon  lowering  the  empty  bottle,  a  current  of  air 
will  be  sucked  in  through  the  short  tube  originally 
blown  into;  this  may  be  regulated  by  the  screw 
pinchcock. 

.  In  inserting  the  gas-sampling  tube  care  should  be 
taken  not  to  insert  it  so  close  to  the  source  of  heat 
as  to  draw  out  the  gases  in  a  dissociated,  i.e.  partly 
decomposed,  condition. 

In  case  of  very  smoky  fuels  it  is  well  to  filter  the 
gases  through  rolls  of  fine  wire  gauze  or  asbestos; 
in  sucking  them  through  a  washing-bottle,  the  water 
may  change  the  composition  of  the  sample. 


CHAPTER    II. 

APPARATUS    FOR    THE   ANALYSIS  OF    CHIMNEY- 
GASES. 

IN  the  writer's  opinion  the  apparatus  which  is  best 
adapted  for  this  purpose  is  that  of  Orsat;  it  is  readily 
portable,  not  liable  to  be  broken,  easy  to  manipulate, 
sufficiently  accurate,  and — in  the  modification  about  to 
be  described — always  ready  for  use,  there  being  no 
stopcocks  to  stick  fast. 

As  the  Bunte  and  Elliott  apparatus  are  also  used 
for  this  purpose,  they  too  will  be  described. 

Fischer's  apparatus,  using  mercury,  is  rather  too 
difficult  for  the  average  engineer;  HempePs  or  More- 
head's*  apparatus  for  the  analysis  of  illuminating-gas 
might  also  be  used;  it  is,  however,  not  customary. 

ORSAT   APPARATUS. 

Description. — The  apparatus  Fig.  8,  is  enclosed  in 
a  case  to  permit  of  transportation  from  place  to  place; 
furthermore,  the  measuring-tube  is  jacketed  with 
water  to  prevent  changes  of  temperature  affecting  the 
gas-volume.  The  apparatus  consists  essentially  of 
the  levelling-bottle  A,  the  burette  B,  the  pipettes 
Pf,  P",  P'",  and  the  connecting  tube  T. 

*  No.  143  Lake  Street,  Chicago. 

II 


12  GAS  AND   FUEL   ANALYSIS. 

Manipulation. —  The  reagents  in  the  pipettes  should 
be  adjusted  in  the  capillary  tubes  to  a  point  on  the 
stem  about  midway  between  the  top  of  the  pipette 
and  the  rubber  connector.  This  is  effected  by  open- 
ing wide  the  pinchcock  upon  the  connector,  the 


FIG.  8.  — ORSAT'S  GAS  APPARATUS. 

bottle  being  on  the  table,  and  very  gradually  lower- 
ing the  bottle  until  the  reagent  is  brought  to  the  point 
above  indicated.  Six  inches  of  the  tubing  used  corre- 
spond to  but  o.i  cc.,  so  that  an  error  of  half  an  inch 
in  adjustment  of  the  reagent  is  without  influence 
upon  the  accuracy  of  the  result.  The  reagents  having 
been  thus  adjusted,  the  burette  and  connecting  tube 
are  completely  filled  with  water  by  opening  d  and 
raising  the  levelling-bottle.  The  apparatus  is  now 


ANALYSIS   OF  CHIMNEY-GASES.  1 3 

ready  to  receive  a  sample  of  gas  (or  air  for  prac- 
tice). In  case  a  flue-gas  is  to  be  analyzed  d  is  con- 
nected with  z,  Fig.  2,  A  lowered  and  about  102  cc. 
of  the  gas  forced  over  by  opening  //;  or  d  may 
be  connected  with  aT  joint  in  the  gas-stream;  the 
burette  after  filling  is  allowed  to  drain  one  minute  by 
the  sand-glass,  c  snapped  upon  its  rubber  tube,  and 
the  bottle  A  raised  to  the  top  of  the  apparatus.  By 
gradually  opening  c  the  water  is  allowed  to  run  into 
the  burette  until  the  lower  meniscus  stands  upon  the 
100  or  o  mark  (according  to  the  graduation  of  the 
apparatus).  The  gas  taken  is  thus  compressed  into 
the  space  occupied  by  100  cc.,  and  by  opening  d  the 
excess  escapes.  Open  c  and  bring  the  level  of  the 
water  in  the  bottle  to  the  same  level  as  the  vvater  in  the 
burette  and  take  the  reading,  which  should  be  100  cc. 
Special  attention  is  called  to  this  method  of  reading: 
if  the  bottle  be  raised,  the  gas  is  compressed;  if 
lowered,  it  is  expanded. 

Determination  of  Carbon  Dioxide. — The  gas  to  be 
analyzed  is  invariably  passed  first  into  pipette  P' ,  con- 
taining potassium  hydrate  for  the  absorption  of  carbon 
dioxide,  by  opening  e  and  raising  A.  The  gas  dis- 
places the  reagent  in  the  front  part  of  the  pipette, 
laying  bare  the  tubes  contained  in  it,  which  being 
covered  with  the  reagent  present  a  large  absorptive 
surface  to  the  gas;  the  reagent  moves  into  the  rear 
arm  of  the  pipette,  displacing  the  air  over  it  into  the 
flexible  rubber  bag  which  prevents  its  diffusion  into 
the  air.  The  gas  is  forced  in  and  out  of  the  pipette 
by  raising  and  lowering^,  the  reagent  finally  brought 
approximately  to  its  initial  point  on  the  stem  of  the 


14  GAS  AND    FUEL   ANALYSIS. 

pipette,  the  burette  allowed  to  drain  one  minute,  and 
the  reading  taken.  The  difference  between  this  and 
the  initial  reading  represents  the  cubic  centimeters  of 
carbon  dioxide  present  in  the  gas.  To  be  certain  that 
all  the  carbon  dioxide  is  removed,  the  gas  should  be 
passed  a  second  time  into  P'  and  the  reading  taken 
as  before;  these  readings  should  agree  within  o.  I  per 
cent. 

Determination  of  Oxygen. — The  residue  from  the 
absorption  of  carbon  dioxide  is  passed  into  the  second 
pipette,  Pff,  containing  an  alkaline  solution  of  potas- 
sium pyrogallate,  until  no  further  absorption  will  take 
place.  The  difference  between  the  reading  obtained 
and  that  after  the  absorption  of  carbon  dioxide,  repre- 
sents the  number  of  cubic  centimeters  of  oxygen 
present. 

Determination  of  Carbonic  Oxide. — The  residue 
from  the  absorption  of  oxygen  is  passed  into  the  third 
pipette,  P'"t  containing  cuprous  chloride,  until  no 
further  absorption  takes  place;  that  is,  in  this  case 
until  readings  agreeing  exactly  (not  merely  to  o.  i)  are 
obtained.  The  difference  between  the  reading  thus 
obtained  and  that  after  the  absorption  of  oxygen, 
represents  the  number  of  cubic  centimeters  of  carbonic 
oxide  present. 

Determination  of  Hydrocarbons — The  residue 
left  after  all  absorptions  have  been  made  may  consist, 
in  addition  to  nitrogen,  the  principal  constituent,  of 
hydrocarbons  and  hydrogen.  Their  determination  is 
difficult  for  the  inexperienced,  and,  if  desired,  a  sample 
of  the  flue-gas  should  be  taken,  leaving  as  little  water 


ANALYSIS   OF  CHIMNEY-GASES.  15 

in  the  apparatus  as  possible,  and  sent  to  a  competent 
chemist  for  analysis. 

Accuracy. — The  apparatus  gives  results  accurate  to 
0.2  of  one  per  cent, 

Time  Required. — About  twenty  minutes  are  re- 
quired for  an  analysis;  two  may  be  made  in  twenty-five 
minutes,  using  two  apparatus. 

Notes. — The  method  of  adjusting  the  reagents  is  the 
only  one  which  has  been  found  satisfactory:  if  the 
bottle  be  placed  at  a  lower  level  and  an  attempt  made 
to  shut  the  pinchcock  c  upon  the  connector  at  the 
proper  time,  it  will  almost  invariably  result  in  failure. 

The  process  of  obtaining  100  cc.  of  gas  is  exactly 
analagous  to  filling  a  measure  heaping  full  of  grain  and 
striking  off  the  excess  with  a  straight-edge;  it  saves 
arithmetical  work,  as  cubic  centimeters  read  off  repre- 
sent percent  directly. 

It  often  happens  when  e  is  opened,  c  being  closed, 
that  the  reagent  in  P'  drops,  due  not  to  a  leak  as  is 
usually  supposed,  but  to  the  weight  of  the  column  of 
the  reagent  expanding  the  gas. 

The  object  of  the  rubber  bags  is  to  prevent  the 
access  of  air  to  the  reagents,  those  in  P"  and  P"r 
absorbing  oxygen  with  great  avidity,  and  hence  if 
freely  exposed  to  the  air  would  soon  become  useless. 

Carbon  dioxide  is  always  the  first  gas  to  be  removed 
from  a  gaseous  mixture.  In  the  case  of  air  the  per- 
centage present  is  so  small,  0.08  to  o.  I,  as  scarcely  to 
be  seen  with  this  apparatus.  It  is  important  to  use 
the  reagents  in  the  order  given ;  if  by  mistake  the  gas 
be  passed  into  the  second  pipette,  it  will  absorb  not 
only  oxygen,  for  which  it  is  intended,  but  also  carbon 


1 6  GAS  AND   FUEL    ANALYSIS. 

dioxide;  similarly  if  the  gas  be  passed  into  the  third 
pipette,  it  will  absorb  not  only  carbonic  oxide,  but 
also  oxygen  as  well. 

The  use  of  pinchcocks  and  rubber  tubes,  original 
with  the  author,  although  recommended  by  Naef,*  is 
considered  by  Fischer, f  to  be  inaccurate.  The  ex- 
perience of  the  author,  however,  does  not  support 
this  assertion,  as  they  have  been  found  to  be  fully 
as  accurate  as  glass  stopcocks,  and  very  much  less 
troublesome  and  expensive. 

In  case  any  potassium  hydrate  or  pyrogallate  be 
sucked  over  into  the  tube  T or  water  in  A,  the  analysis 
is  not  spoiled,  but  may  be  proceeded  with  by  connect- 
ing on  water  at  d,  opening  this  cock,  and  allowing  the 
water  to  wash  the  tubes  out  thoroughly.  The  addi- 
tion of  a  little  hydrochloric  acid  to  the  water  in  the 
bottle  A  will  neutralize  the  hydrate  or  pyrogallate,  and 
the  washing  may  be  postponed  until  convenient. 

After  each  analysis  the  number  of  cubic  centimeters 
of  oxygen  and  carbonic  oxide  should  be  set  down  upon 
the  ground-glass  slip  provided  for  the  purpose.  By 
adding  these  numbers  and  subtracting  their  sum  from 
the  absorption  capacity  (see  Reagents)  of  each  reagent, 
the  condition  of  the  apparatus  is  known  at  any  time, 
and  the  reagent  can  be  renewed  in  season  to  prevent 
incorrect  analyses. 

BUNTE   APPARATUS. 

Description. — The  apparatus  Fig.  9  consists  of  a 
burette — bulbed  to  avoid  extreme  length — provided 

*  Wagner's  Jahresb.  1885,  p.  423. 

f  Technologic  d.  Brennstoffe,  foot  note  p.  295, 


ANALYSIS   OF  CHIMNEY-GASES. 


at  the  top  with  a  funnel  F  and  three-way  cocky,  and 
a  cock  /  at  the  bottom.  These  stopcocks  are  best 
of  the  Greiner  and  Friedrichs  obliquely  bored  form. 
The  burette  is  supported  upon  a  retort- 
stand  with  a  spring  clamp. 

A  "  suction-bottle  "  S,  an  8-oz.  wide- 
mouthed  bottle,  fitted  similarly  to  a 
wash-bottle,  except  that  the  delivery- 
tube  is  straight  and  is  fitted  with  a 
four-inch  piece  of  J-inch  black  rubber 
tubing,  serves  to  withdraw  the  re- 
agents and  water  when  necessary,  A 
reservoir  to  contain  water  at  the  tem- 
perature of  the  room,  fitted  with  along 
rubber  tube,  should  be  provided  for 
washing  out  the  reagents  and  filling 
the  burette. 

Manipulation.  --  Before  using  the 
apparatus,  the  keys  of  the  stopcocks 
should  be  taken  out,  wiped  dry,  to- 
gether with  their  seats,  and  sparingly 
smeared  with  vaseline  or  a  mixture  of 
vaseline  and  tallow  and  replaced.  The  FIG.  9.— BUNTE'S 
completeness  of  the  lubrication  can  be  GAS  ApPARATUS- 
judged  by  the  transparency  of  the  joint,  a  thoroughly 
lubricated  joint  showing  no  ground  glass.  The 
burette  is  filled  with  water  by  attaching  the  rubber 
tube  to  the  tip  at  /  and  opening  the  stopcocks  at  the 
top  and  bottom  ;  j  is  connected  with  the  source  whence 
the  gas  is  to  be  taken,  turned  to  communicate  with 
the  burette  and  opened,  about  102  cc.  of  gas  allowed 
to  run  in,  and  j  and  /closed. 


1 8  GAS  AND    FUEL   ANALYSIS. 

The  cup  F  is  filled  with  water  to  the  25-00.  mark^y 
turned  to  establish  communication  between  it  and  the 
burette,  the  burette  allowed  to  drain  one  minute  by 
the  sand-glass,  and  the  reading  taken,  the  cup  being 
refilled  to  the  mark  if  necessary.  The  readings  are 
thus  taken  under  the  same  pressure  each  time,  i.e., 
this  column  of  water  plus  the  height  of  the  barometer; 
and  as  the  latter  is  practically  constant  during  the 
analysis,  no  correction  need  be  applied,  it  being  within 
the  limits  of  error. 

Determination  of  Carbon  Dioxide. — The  "  suc- 
tion-bottle "  is  connected  with  the  tip  of  the  burette, 
/  opened,  and  the  water  carefully  sucked  out  nearly  to 
/.  The  bottle  is  now  disconnected,  the  burette  dis- 
mounted from  its  clamp,  using  the  cup  as  a  handle, 
and  the  25  cc.  of  water  turned  out.  The  tip  is 
immersed  under  potassium  hydrate  contained  in  the 
No.  3  porcelain  dish,  and  the  cock  /  opened,  then 
closed,  and  the  tip  wiped  clean  with  a  piece  of  cloth. 
The  burette  is  now  shaken,  holding  it  by  the  tip  and 
the  cup,  the  thumbs  resting  upon  /  and  /;  more 
reagent  is  introduced,  the  absorption  of  the  gas  caus- 
ing a  diminished  pressure,  and  the  operation  repeated 
until  no  change  takes  place.  The  cup  is  now  filled 
with  water,  j  opened,  and  the  reagent  completely 
washed  out  into  an  ordinary  tumbler  placed  beneath 
the  burette.  Four  times  filling  of  .F  should  be  suffi- 
cient for  this  purpose.  The  cup  is  now  filled  to  the 
25-cc.  mark,  j  opened,  and  the  reading  taken  as 
before. 

The  difference  between  this  reading  and  the  initial 
represents  the  number  of  cubic  centimeters  of  carbon 


ANALYSIS   OF   CHIMNEY-GASES.  1 9 

dioxide;  this  divided  by  the  volume  of  the  gas  taken 
gives  the  per  cent  of  this  constituent. 

Determination  of  Oxygen. — The  water  is  again 
sucked  out,  and  potassium  pyrogallate  solution  intro- 
duced, similarly  to  potassium  hydrate;  this  is  dis- 
placed by  water,  and  the  reading  taken  as  before. 
The  difference  between  this  and  the  last  reading  is  the 
volume  of  oxygen  present. 

Determination  of  Carbonic  Oxide. — The  water  is 
removed  for  a  third  time,  and  acid  cuprous  chloride 
solution  introduced  and  the  absorption  made  as  before; 
this  is  washed  out,  first  with  water  containing  a  little 
hydrochloric  acid  to  dissolve  the  white  cuprous  chlo- 
ride which  is  precipitated  by  the  addition  of  water, 
and  finally  with  pure  water,  and  the  reading  taken  as 
before.  The  difference  between  this  and  the  preced- 
ing gives  the  volume  of  carbonic  oxide  present. 

Notes. — Especial  care  should  be  taken  not  to  grasp 
the  burette  by  the  bulb,  as  this  warms  the  gas  and 
renders  the  readings  inaccurate.  The  stopcocks  can 
conveniently  be  kept  in  the  burette  by  elastic  bands 
of  suitable  size.  When  the  apparatus  is  put  away  for 
any  considerable  time,  a  piece  of  paper  should  be 
inserted  between  the  key  and  socket  of  each  stopcock 
to  prevent  the  former  from  sticking  fast.  To  ascer' 
tain  when  the  absorption  is  complete,  the  burette  is 
mounted  in  its  clamp  and  allowed  to  drain  until  the 
meniscus  is  stationary,  the  dish  containing  the  reagent 
raised  until  the  tip  is  covered,  /opened,  and  any  change 
in  level  noted.  If  the  meniscus  rises,  the  absorption 
is  incomplete  and  must  be  continued;  if  it  remains 
stationary  or  falls,  the  absorption  may  be  regarded  as 


20  GAS  AND    FUEL   ANALYSIS. 

finished.  In  case  the  grease  from  the  stopcocks 
becomes  troublesome  inside  the  burette,  it  may  be 
removed  by  dissolving  it  in  chloroform  and  washing 
out  with  alcohol  and  then  with  water.  The  object  in 
sucking  the  water  not  quite  down  to  /,  thus  leaving  a 
little  water  in  the  burette,  is  to  discover  if  /  leaks,  the 
air  rushing  in  causes  bubbles. 

The  object  in  washing  out  each  reagent  and  taking 
all  readings  over  water  is  to  obviate  corrections  for 
the  tension  of  aqueous  vapor  over  potassium  hydrate, 
hydrochloric  acid,  or  any  of  the  reagents  which  might 
be  employed.  The  tension  of  aqueous  vapor  over 
seven  per  cent  caustic  soda  is  less  than  over  water. 

Accuracy  and  Time  Required. — The  apparatus  is 
rather  difficult  to  manipulate,  but  fairly  rapid — about 
twenty-five  minutes  being  required  for  an  analysis — 
and  accurate  to  one  tenth  of  one  per  cent. 

ELLIOTT   APPARATUS. 

Description. — The  apparatus  Fig.  10  consists  of  a 
burette  holding  100  cc.  graduated  in  tenths  of  a  cubic 
centimeter  and  bulbed  like  the  Bunte  apparatus — the 
bulb  holding  about  30  cc. ;  it  is  connected  with  a 
levelling-bottle  similar  to  the  Orsat  apparatus.  The 
top  of  the  burette  ends  in  a  capillary  stopcock,  the 
stem  of  which  is  ground  square  to  admit  of  close  con- 
nection with  the  "laboratory  vessel,"  an  ungraduated 
tube  similar  to  the  burette,  except  of  125  cc.  capacity. 
The  top  of  this  "vessel  "  is  also  closed  with  a  capil- 
lary stopcock,  carrying  by  a  ground-glass  joint  a 
thistle-tube  F,  for  the  introduction  of  the  reagents. 
The  lower  end  of  this  "  vessel  "  is  closed  by  a  rubber 


ANALYSIS   OF  CHIMNEY-GASES. 


21 


stopper  carrying  a  three-way  cock  <?,   and   connected 
with    a    levelling-bottle    D.       The 
burette  and  vessel  are   held  upon  a  H?\ 

block  of  wood — supported  by  a  ring 
stand — by  fine  copper  wire  tight- 
ened by  violin  keys. 

Manipulation. — The  ground-glass  (c.c)  '  / 
joints  are  lubricated  as  in  the  Bunte 
apparatus.  The  levelling-bottles  are 
filled  with  water,  the  stopcocks 
opened,  and  the  bottles  raised  until 
the  water  flows  through  the  stop- 
cocks m  and  n.  m  is  connected 
with  the  source  whence  the  gas  to 
be  analyzed  is  to  be  taken,  n  closed, 
D  lowered  and  rather  more  than  100 
cc.  drawn  in,  and  m  closed,  n  is 
opened,  D  raised  and  E  lowered, 
nearly  100  cc.  of  gas  introduced, 
and  ;/  closed;  by  opening  m  and 
raising  D  the  remainder  of  the  gas 
is  allowed  to  escape,  the  tubes  being 
filled  with  water  and  m  closed,  n  is 
opened  and  the  water  brought  to 
the  reference-mark;  the  burette  is 
allowed  to  drain  one  minute,  the 
level  of  the  water  in  E  is  brought 
to  the  same  level  as  in  the  burette, 
and  the  reading  taken. 

Determination  of  Carbon  Dioxide — By  raising  E, 
opening  #,  and  lowering  D,  the  gas  is  passed  over  into 
the  laboratory  vessel;  F  is  filled  within  half  an  inch 


FIG.  10. — ELLIOTT 
GAS  APPARATUS. 


22  GAS  AND   FUEL   ANALYSIS. 

of  the  top  with  potassium  hydrate,  o  closed,  m  opened, 
and  the  reagent  allowed  to  slowly  trickle  in.  A  No.  3 
evaporating-dish  is  placed  under  o,  and  this  turned  to 
allow  the  liquid  in  the  laboratory  vessel  to  run  into 
the  dish.  At  first  this  is  mainly  water,  and  may  be 
thrown  away;  later  it  becomes  diluted  reagent  and 
may  be  returned  to  the  thistle-tube.  When  the 
depth  of  the  reagent  in  the  thistle-tube  has  lowered 
to  half  an  inch,  it  should  be  refilled  either  with  fresh 
or  the  diluted  reagent  and  allowed  to  run  in  until  the 
absorption  is  judged  to  be  complete,  and  the  gas 
passed  back  into  the  burette  for  measurement.  To 
this  end  close  o  and  then  ;«,  raise  E,  open  n,  and 
force  some  pure  water  into  the  laboratory  vessel,  thus 
rinsing  out  the  capillary  tube.  Now  raise  D  and  lower 
£,  shutting  n  when  the  liquid  has  arrived  at  the  refer- 
ence-mark. The  burette  is  allowed  to  drain  a  minute, 
the  level  of  the  water  in  the  bottle  E  brought  to  the 
same  level  as  the  water  in  the  burette,  and  the  reading 
taken. 

Determination  of  Oxygen. — The  manipulation  is 
the 'same  as  in  the  preceding  determination,  potassium 
pyrogallate  being  substituted  for  potassium  hydrate; 
the  apparatus  requiring  no  washing  out. 

Determination  of  Carbonic  Oxide. — The  labora- 
tory vessel,  thistle-tube,  and  bottle  if  necessary,  are 
washed  free  from  potassium  pyrogallate  and  the 
absorption  made  with  acid  cuprous  chloride  similarly 
to  the  determination  of  carbon  dioxide.  The  white 
precipitate  of  cuprous  chloiide  may  be  dissolved  by 
hydrochloric  acid. 


ANALYSIS   OF  CHIMNEY-GASES.  2$ 

Accuracy  and  Time  Required. — The  apparatus  is 
as  accurate  for  absorptions  as  that  of  Orsat;  it  is 
stated  to  be  much  more  rapid — a  claim  which  the  writer 
cannot  substantiate.  It  is  not  as  portable,  is  more 
fragile,  and  more  troublesome  to  manipulate,  and  as 
the  burette  is  not  jacketed  it  is  liable  to  be  affected 
by  changes  of  temperature. 

Notes. — In  case  at  any  time  it  is  desired  to  stop 
the  influx  of  reagent,  o  should  be  closed  first  and 
then  m\  the  reason  being  that  the  absorption  may 
be  so  rapid  as  to  suck  air  in  through  o,  m  being 
closed. 

The  stopcock  should  be  so  adjusted  as  to  cause  the 
reagent  to  spread  itself  as  completely  as  possible  over 
the  sides  of  the  burette. 

By  the  addition  of  an  explosion-tube  it  is  used  for 
the  analysis  of  illuminating-gas,*  bromine  being  used 
to  absorb  the  "  illuminants."  Winklerf  states  that  this 
absorption  is  incomplete;  later  work  by  Treadwell  and 
Stokes,  and  also  Korbuly,  %  has  shown  that  bromine  water, 
by  a  purely  physical  solution,  does  absorb  the  "  illumi- 
nants "  completely;  Hempel  §  states  that  explosions  of 
hydrocarbons  made  over  water  are  inaccurate,  so  that 
the  apparatus  can  be  depended  upon  to  give  results  upon 
methane  and  hydrogen  only  within  about  two  per  cent. 

*  Mackintosh,  Am.  Chem.  Jour.  9,  294. 

f  Zeit.  f.  Anal.  Chem.  28,  286. 

%  TreadwelPs  Quan.  Analysis  (Hall's  translation),  p.  569. 

§  Gasanalytische  Methoden,  p.  102. 


24  GAS   AND  FUEL   ANALYSIS. 

GAS-BALANCES. 

Under  this  heading  are  included  various  devices 
either  for  weighing  a  volume  of  the  chimney-gas,  as 
the  Econometer  of  Arndt,*  or  weighing  a  globe  in  an 
atmosphere  of  the  gas,  as  the  Gas-balance  of  Custodis.f 
The  Gas-composimeter  of  Uehlingf  depends  upon 
the  laws  governing  the  flow  of  gases  through  small 
apertures. 

They  are  difficult  to  adjust  and  keep  in  adjustment, 
requiring  to  be  checked  frequently  by  the  Orsat  appa- 
ratus, and  are  expensive.  Their  indications  are  within 
about  half  of  one  per  cent  of  those  given  by  the 
chemical  apparatus.  Only  the  presence  of  carbon  di- 
oxide is  indicated  by  them. 

*  Zeit.  d.  Vereins  deutsch.  Ingenieure,  37,  801. 

f  Gill,   Engine  Room  Chemistry,  pp.  96  and  97. 

J  Poole,  Calorific  Power  of  Fuels,  p.  150,  26.  edition  (1900). 


CHAPTER   III. 

-• 

MEASUREMENT  OF   TEMPERATURE. 

IN  the  majority  of  cases,  the  ordinary  mercurial 
thermometer  will  serve  to  determine  the  temperature 
of  the  chimney-gases.  It  should  not  be  inserted  naked 
into  the  flue,  but  be  protected  by  a  bath  of  cylinder, 
or  raw  linseed  oil,  contained  in  a  brass  or  iron  tube. 
These  tubes  may  be  half  an  inch  inside  diameter  and 
two  to  three  feet  in  length.  Temperatures  as  high  as 
625°  C.  have  been  observed  in  chimneys;  this  lasts  of 
course  but  for  a  moment,  but  would  be  sufficient  to 
burst  the  unprotected  thermometer. 

For  the  observation  of  higher  temperatures,  recourse 
must  be  had  to  the  "  high-temperature  thermom- 
eters," filled  with  carbon  dioxide  under  a  pressure  of 
about  one  hundred  pounds,  giving  readings  to  550°  C.* 
These  may  be  obtained  of  the  dealers  in  chemical 
apparatus;  some  require  no  bath,  being  provided 
with  a  mercury-bath  carefully  contained  in  a  steel 
tube,  and  the  whole  enclosed  in  a  bronze  tube.f 

*  Those  made  by  W.  Apel,  Gottingen,  Germany^  are  about  three 
feet  long,  the  scale  occupying  about  one  foot,  thus  avoiding  the 
necessity  of  withdrawing  the  thermometer  from  the  bath  for 
reading.  H.  J.  Green  of  Brooklyn,  N.  Y.,  makes  similar  ones. 

f  Hohmann  Special  Thermometers,  made  by  Hohmann  and  Maurer 
Co.,  44  High  Street,  Boston,  Mass. 

25 


26  GAS  AND   FUEL   ANALYSTS. 

These  thermometers  should  be  tested  from  time  to 
time  either  by  comparison  with  a  standard  or  by  inser- 
tion in  various  baths  of  a  definite  temperature.  Some 
of  the  substances  used  for  these  baths  are:  water,  boil- 
ing-point 100° ; naphthalene,  Bpt.  2 1 8°;  benzophenon, 
Bpt.  306°;  and  sulphur,*  Bpt.  445°.  Care  should  be 
taken  that  the  bulb  of  the  thermometer  does  not  dip 
into  the  melted  substance,  but  only  into  the  vapor, 
and  that  the  stem  exposure  be  as  nearly  as  possible 
that  in  actual  use. 

For  the  measurement  of  temperatures  beyond  the 
range  of  these  thermometers  the  Le  Chatelier  thermo- 
electric pyrometer  may  be  used.  This  consists  of  a 
couple  formed  by  the  junction  of  a  platinum  and 
platinum- 10$  rhodium  wire,  passing  through  fire-clay 
tubes  in  a  porcelain  or  iron  envelope  and  connected 
with  a  galvanometer.  The  hotter  the  junction  is 
heated  the  greater  the  current  and  the  galvanometer 
deflection;  this  latter  is  determined  for  several  points, 
naphthalene,  sulphur,  and  copper,  Mpt.  1083°  C.,  or 
even  platinum,  1753°  C.,  and  a  plot  made  with  gal- 
vanometer-readings as  abscissae  and  temperatures  as 
ordinates.  From  this  the  temperature  corresponding 
to  any  deflection  is  readily  obtained. 

The  exact  description  of  the  instrument  and  details 
of  calibration  are,  however,  beyond  the  scope  of  this 
work,  and  the  student  is  referred  for  these  to  articles 
by  Le  Chatelier,  Societe  Technique  de  1'Industrie  du 
Gaz,  1890,  abstracted  in  Jour.  Soc.  Chem.  Industry, 

*  In  testing  the  Hohmann  thermometers  in  sulphur-vapor,  the 
bronze  tube  should  be  prevented  from  corrosion  by  the  vapor  by 
a  glass  envelope. 


MEASUREMENT   OF    TEMPERATURE. 


27 


9,  326,  and  Holman,  Proc.  Am.  Academy,  1895,  p. 
234;  later  works  are  those  of  Burgess  and  Le  Chatelier 
and  Boudouard,  ''High  Temperature  Measurements" 
(1912),  and  also  C.  L.  Norton,  "  Notes  on  Heat  Meas- 
urements" (1902). 

An  error  of  5°  in  the  reading  of  the  thermometer 
affects  the  final  result  by  about  20  calories. 

In  case  neither  of  these  methods  be  available  nor 


300 


FIG.  ii. — MELTING-POINT  BOXES. 

applicable,  use  may  be  made  of  the  melting-points 
of  certain  metals  or  salts  contained  in  small  cast-iron 
boxes,  Fig.  n.  The  melting-points  of  certain  metals 
and  salts  are  given  in  Table  VII. 


CHAPTER    IV. 
CALCULATIONS. 

As  has  been  already  stated  in  the  Introduction,  the 
object  of  analyzing  the  flue-gases  is  to  ascertain,  first, 
the  completeness  of  the  combustion,  especially  the 
amount  of  air  which  has  been  used  or  the  "  pounds  of 
air  per  pound  of  coal,"  and  second,  the  amount  of 
heat  passing  up  chimney. 

i.  To  Ascertain  the  Number  of  Pounds  of  Air 
per  Pound  of  Coal. — A  furnace-gas  gives  11.5$  CO2, 
7.4$  O,  o.gfo  CO,  and  80.2$  N.  Data:  atomic  weights, 
O  =  16,  C  =:  12;  weight  liter  CO2  —  1.966  grs.,  of 
O,  1.43  grs.,  of  CO,  1.251  grs.  Find  the  number  of 
grams  of  each  constituent  in  100  liters  of  the  furnace- 
gas,  and  from  this  the  weight  of  carbon  and  weight  of 
oxygen.  11.5  (liters  CO2)  X  1.97  (wt.  liter  CO2)  = 

32/  O  \ 
22.66  grms.  CO2;  now  — \r^~ )  °f  this  !'s  oxygen  = 

16.48  grms.,  6.18  grms.  is  carbon.  The  weight  of 
free  oxygen  is  7.4  X  1.43  =  10.58  grms.  The  weight 
of  carbon  and  oxygen  in  the  carbonic  oxide  is  0.9  X 

i6/  O  N. 
1.25  =  1. 12  grms.  CO.     Now      !  —  \is  oxygen  or  0.64 

grm.,  and  0.48  grm.  is  carbon.  There  are  then  pres- 
ent in  100  liters  of  the  gas  27.70  grms.  oxygen  and 
6.66  grms.  caibon;  corresponding  to  120.0  grms.  air 

28 


CALCULATIONS.  2Q 

to  6.66  grms.   carbon,    air  being  23.  i#   oxygen    by 

grms.  )  grm.  ) 

weight;    or  18.02   *          j  air  per  lb       |  carbon. 

the  coal  be  83^  carbon,  this  figure  must  be  diminished 
accordingly,  giving  in  this  case  14.95  Ibs.  air  per  lb. 
of  coal.  Theory  requires  11.54  Ibs.  air  per  lb.  of  car- 
bon, but  in  practice  the  best  results  are  obtained  by 
increasing  this  from  50$  to  100^.* 

2.  To  Ascertain  the  Quantity  of  Heat  Passing 
,ip  Chimney  — Determine  the  volume  of  gas  generated 
jrom  one  kilo  of  coal  when  burned  so  as  to  produce 
the  gas  the  analysis  of  which  has  just  been  made 
according  to  the  directions  given.  The  chemical 
analysis  of  the  coal  is  as  follows:  moisture  1.5$, 
sulphur  i.2#,  carbon  83^,  hydrogen  2.5^,  ash  11.4^, 
oxygen  and  nitrogen  (by  difference)  0.4$.  Then 
there  are  in  one  kilo  of  coal  830  grms.  carbon,  of 
this  suppose  but  800  to  be  burned,  the  remaining  30 
grms.  going  into  the  ash;  of  the  800  grms.  618/666 
or  742  grms.  produced  carbon  dioxide,  and  48/666 
or  58  grms.  produced  carbonic  oxide.  From  6.18 
grms.  carbon  were  produced  11.5  liters  carbon  di- 
oxide in  the  problem  in  I ;  hence  742  grms.  would 
furnish  1381  liters.  6. 18  :  742  :  :  1 1.5  :  y.  y=i$8i. 
Similarly  58  grms.  carbon  would  furnish  109.0  liters 
carbonic  oxide.  0.48  :  58  ::  0.90  :  z.  2=109.0.  The 
volume  of  oxygen  can  be  found  by  the  proportion 
11.5  (#CO2):  7.4  (#O)::  1381  :  x.  x  =  888  liters.  In 
the  same  manner  the  nitrogen  is  found  to  be  9631 
liters.  1 1.5  :  80.2  :  :  1381  :  //.  14=9631.  One  kilo  of 
coal  under  these  conditions  furnishes  1.381  cu.  meters 

*  Schearer-Kestner,  Jour.  Soc.  Chem.  Industry,  7,  616.  0.75  lb. 
per  1000  B.t.u.  Nisbet,  Power.  36,  995  (1912). 


3O  GAS   AND    FUEL    ANALYS/S. 

carbon  dioxide,   0.109   c-   m-   carbonic    oxide,   O.888 
c.  m.  oxygen,  and  9.631  c.  m.  nitrogen. 

The  quantity  of  heat  carried  off  by  each  gas  is  its 
rise  of  temperature  X  its  weight  X  its  specific  heat, 
The  specific  heats  of  the  various  gases  are  shown  in 
the  table  below,  and  for  facility  in  calculation,  a  column 
is  given  obtained  by  multiplying  the  weight  by  the 
specific  heat;  multiplying  the  volumes  obtained  in  the 
previous  calculation  by  the  numbers  in  this  column 
and  by  the  rise  in  temperature  gives  the  number  of 
calories  (C)  that  each  gas  carries  away. 

TABLE    OF   SPECIFIC    HEATS   OF   VARIOUS    GASES.* 

Wt.  of  Cu.  M.     Sp.  HeatX 
Name  of  Gas.  Sp.  Heat.  Rg  Wt.ofCu.M.      L°g' 

Carbon  dioxide  (io°-35o°).  0.234  r-97  0.463  9.6656 

"        monoxide 0.245  1.26  0.308  9.4886 

Oxygen 0.217  1.43  0.311  9.4928 

Nitrogen 0.244  1.26  0.306  9.4857 

Aqueous  vapor 0.480  0.80  0.387  9-5877 

In  the  test  the  average  temperature  of  the  escaping 
gases  was  275°  C. ;  that  of  the  air  entering  the  grate 
was  25°  C.,  a  rise  of  temperature  of  250°  C.  As 
shown  by  the  wet-and-dry-bulb  thermometer,  the  air 
was  50  per  cent  saturated  with  moisture. 

The  calculation  of  the  heat  carried  away  is  then  for: 

Cu.  M.  C. 

Carbon  dioxide 1.381  X  250  X  0.463  =  160.0 

Carbonic  oxide o.  109  X     "    X  0.308  =       8.4 

Oxygen 0.888  X     "    X  0.311  =    69.1 

Nitrogen 9.631  X     "    X  0.306 •=  737.0 


Total 12.009  974-5 


Fischer,  Tech.  d.  Brennstoffe,  p.  267. 


CA LCULA  TIONS.  3  I 

There  is,  however,  another  gas  passing  up  chimney 
of  which  we  have  taken  no  cognizance,  namely,  water- 
vapor;  this  comes  from  the  moisture  in  the  coal,  from 
the  combustion  of  hydrogen  in  the  coal,  and  from  the 
air  entering  the  grate;  its  volume  is  calculated  as 
follows: 

The  moisture  in  the  coal  as  found  by  chemical 
analysis  was  1.5$  =  0.015  kg.;  the  hydrogen  in  the 
coal  was  2.5$  =  0.025  kg.  The  amount  of  water  this 
forms  when  burned  is  nine  times  its  weight,  0.025  kg. 
X  9  =  0.225  kg.  The  moisture  in  the  air  entering  the 
grate  would  be,  if  completely  saturated,  22.9  grams 
per  cubic  meter,  as  shown  by  Table  I ;  it  was,  how- 
ever, but  50$  saturated.  The  quantity  is  then,  the 
volume  of  air  used  per  kilogram  of  coal  X  moisture 
contained  in  it,  or  12.009  X  22.9  X  0.50  =  o,  137  kg. 
The  weight  of  aqueous  vapor  passing  up  chimney  per 
kilogram  of  coal  is  0.015  -|-  0.225  -j-  0.137  =  0.377 
kg.  ;  the  quantity  of  heat  that  this  carries  off  is  0.377 
X  250  X  0.480  =  45.2  C.  The  total  quantity  of  heat 
passing  up  chimney  is  then  1019.7  C.  The  heat  of 
combustion  of  this  coal  as  found  by  Mahler's  calori- 
metric  bomb  was  7220  C. ;  hence  the  percentage  of 
heat  carried  off  is  1020/7220  =  14.  i#. 

The  preceding  calculations  though  correct  are 
tedious,  so  much  so,  as  to  almost  preclude  their  use 
for  an  hourly  observation  of  the  firing.  They  should 
be  employed,  however,  in  making  the  final  calculation 
of  a  boiler-test,  using  the  averages  obtained. 

Shields  *  has  combined  the  operations  in 

*  Power,  1908. 


32  GAS  AND   FUEL   ANALYSIS. 

I.    Pounds  of  Air  per  Pound  of  Coal  (p.  28),  and 
obtains  the  following  formula: 
Pounds  of  air  per  pound  of  coal 

Per  cent,  carbon  in  coal 
2'3IPer  cent.  CO2  +  per  cent.  CO. 
Similarly,  Per  cent,  heat  lost 
Per  cent,  carbon  in  coal  200  + per  cent.  CC>2 

"  HeatingTalue  of  coal  X  Per  cent.  CO2  +  percent.COX 
rise  in  temperature  in  °C.  X  0.2864. 

The  values  found  by  this  equation  are  0.5  per  cent,  low, 
as  no  cognizance  has  been  taken  of  the  water  vapor. 

In  rapid  work  the  following  formula  will  be  found 
more  applicable:  Let  o  and  n  represent  the  percent- 
ages of  oxygen  and  nitrogen  found  in  the  chimney- 
gas;  then  the  ratio  of  the  air  actually  used  to  that 
theoretically  necessary  is  expressed  by  the  formula. 


21  — 


Applying    it    in  the    case    of    the    flue-gas    given,   it 
becomes 


80.2 

Multiplying  this  by  11.54,  the  theoretical  number  of 
pounds  of  air  per  pound  of  carbon,  we  obtain  17.69  as 
against  18.02  on  page  28. 

Bunte  *  has  given  a  shorter  method  for  the  deter- 


*  Jour.   f.    Gasbeleuchtung,   43,   637  (1900)  ;  Abstr.   Jour.  Soc. 
"Ch'fti.  Industry,  19,  887. 


TAB 

BUNTE'S    CHART   SHOWING    HEAT   LOST    IN    CHIJV 

TEMPE 


co2Q 

-19 


10 


PER 
40 


2376  -18 

2255  -n 

2131  -16 

2004  15 

1877  14 

1753  13 

1623  13 

o  1493  11 

LJ 

2  1361  10 


ui 

I    1229      9 


1096 


830  6 
694  5 
557  4 
418  3 
881  2 
141  -1 

o-o 


\\ 


\  \ 


\ 


\  X 


\ 


\ 


XX 


X 


XX 


V 


\\ 


100 


yo 


80 


70 


PER 


i  x. 

£Y -GASES    FROM    THE    CARBONIC    ACID    AND    THE 
.TURE. 


TICIENCY 


3500 


10  0 

To  face  page  33. 


f 


TABLE  XL 


ACTUAL  TEMPERATURES 


.:..vr 


CALCULATIONS. 


33 


mination  of  the  quantity  of  heat  passing  up  chimney, 
and  one  which  does  not  involve  the  analysis  of  the 
coal. 

For  every  per  cent  of  carbonic  acid  present  43.43  C. 
per  cubic  meter  of  flue-gases  have  been  developed  =  W\ 
C—  specific  heat  of  the  flue-gases  per  cubic  meter; 
then  W/C  represents  the  initial  temperature  (which  is 
never  attained)  the  ratio  of  which  t'o  the  actual  exit 
temperature  of  the  flue-gases  shows  the  heat  lost.  If 
T  —  this  initial  temperature  and  /  the  rise  of  tempera- 
ture of  the  flue-gases,  then  t/T  represents  the  heat 
lost  in  the  chimney-gases. 

The  following  table  gives  the  data  for  the  calculation 
for  both  pure  carbon  and  coal  of  average  value. 


Per  Cent  of 
PO     in 

Specific  Heat 
of 

Initial  Temperature.  W/C.    Degrees  C. 

J^vJg    *"• 

Chimney  Gas. 

Chimney  Gas. 

For  Carbon 

For  Coal 

Diff.  for 

=   '/'. 

=   T. 

0.1%  CO,. 

.1 

0.308 

141 

I67 

tf\ 

2 

0.310 

280 

331 

1  0 

16 

3 

0.311 

419 

493 

T^ 

4 

0.312 

557 

652 

ID 

5 

0.313 

694 

808 

15 

6 

0.314 

830 

961 

15 

7 

0.315 

962 

III2 

15 

8 

0.316 

1096 

I26l 

15 

9 

0.318 

1229 

1407 

:5 

TO 

0.319 

1360 

1550 

*4 

II 

0.320 

1490 

1692 

J4 

12 

0.322 

1620 

1830 

T4 

13 

0.323 

1750 

1968 

J4 

14 

0.324 

1880 

2IO2 

T3 

15 

0.324 

2005 

2237 

T3 

16 

0.325 

2130 

2366 

13 

Applying  this  to  the  problem   on  page  29  we  find 
the  initial  temperature    T  to  be  1762°  C.,  the  rise  of 


34  GAS  AND    FUEL   ANALYSIS. 

temperature  of  the  gases  was  250°  C.,  the  loss  is 
250/1762  =  14.2$,  against  14.1$  found  by  the  calcu- 
lation page  31. 

Bunte  also  employs  a  partially  graphical  method  for 
the  determination  of  the  loss  of  heat.  In  Table  X 
the  extreme  left-hand  column  represents  the  tempera- 
tures which  should  be  obtained  by  the  combustion  of 
the  average  coal  with  the  formation  of  a  chimney-gas 
containing  the  percentages  of  carbon  dioxide  in  the 
column  next  it.  Applying  this  to  our  case  we  find 
the  theoretical  temperature  for  11.5$  CO2  to  be  1558°; 
dividing  the  rise  of  temperature  actually  observed  — 
250°  —  by  this,  we  obtain  16.05$,  or  2<f°  more  than  by 
the  method  of  page  31. 

Almost  the  identical  result  can  be  obtained  from 
Table  XI  directly  :  if  the  point  of  intersection  of  the 
diagonal  representing  the  per  cent  of  carbon  dioxide 
with  the  horizontal  line  denoting  the  actual  tem- 
perature, on  the  right,  be  followed  to  the  bottom  of 
the  table  the  per  cent  of  loss  is  ascertained. 

Table  XI  is  the  lower  right-hand  corner  of  Table  X 
enlarged. 

W.  A.  Noyes*  states  that  the  following  formula 
gives  close  results  and  is  also  independent  of  the  com- 
position of  the  coal. 


Percentage  loss  =  (o.on-j  ---  —  ^  —  -0.00605  H 

L,U  / 


/'—  0- 


Lunge  f  has  also  given  a  shorter  method  for  the  cal 
culation  of  the  heat  lost. 

*  Am.  Chem.  Journal,  19,  162. 

f  Zeit.  f.  angewandte  Chemie,  1889,  240. 


CALCULATIONS.  35 

The  following  table  *  shows  roughly  the  excess  of  air 
and  the  per  cent  of  heat  lost  in  the  chimney  gases: 

PER  CENT  OF   CARBONIC  ACID. 

2      3     4     5     6     7     8      9     10    ii    12    13    14    15 

VOLUME   OF   AIR   MORE   THAN   THEORY. 
(Theory— i. o). 

9-5  6-3  4-7  3-8  3-2  2.7  24  2.1  1.9  1.7  1.6  1.5  1.4  1.3 

PER    CENT     LO2S     OF     HEAT. 
Temp,  of  chimney  gases,  518°  F. 

go   60  45   36  30   26    23    20   18    16    15    14    13    12 

Determination  of  Loss  Due  to  Formation  of  Car- 
bonic Oxide. — On  page  29  we  see  that  58  grams  of 
carbon  burned  to  carbonic  oxide;  for  every  gram  of 
carbon  burned  to  carbonic  oxide  there  is  a  loss  of 
5.66  C.,  in  this  case  a  loss  of  328  C.  The  heating  value 
of  the  coal  is  7220  C.,  hence  the  loss  is  4.5  per  cent. 

*  Arndt's  Econometer  Circular. 


CHAPTER  V. 

APPARATUS    FOR   THE   ANALYSIS   OF    FUEL    AND 
ILLUMINATING   GASES. 

HEMPEL'S  APPARATUS. 

Description. — The  apparatus,  Figs.  12  and  13,  is 
very  similar  in  principle  to  that  of  Orsat ;  the  burette 
is  longer,  admitting  of  the  reading  of  small  quantities 
of  gas,  and  the  pipettes  are  separate  and  mounted  in 
brass  clamps  on  iron  stands.  P  shows  a  "simple" 
pipette*  provided  with  a  rubber  bag;  this  form,  after 
ten  years  of  use,  can  be  said  to  satisfactorily  take  the 
place  of  the  cumbersome  "compound  "  pipette. 

The  pipette  for  fuming  sulphuric  acid  f  is  shown  at 
F,  and  differs  from  the  ordinary  in  that  vertical  tubes 
after  the  manner  of  those  in  the  Orsat  pipettes  replace 
the  usual  glass  beads.  This  prevents  the  trapping  of 
any  gas  by  the  filling,  which  was  so  common  with  the 
beads  and  glass  wool.  E  represents  the  large  explo- 
sion pipette,^;  of  about  250  cc.  capacity,  with  walls  half 
an  inch  thick ;  the  explosion  wires  enter  at  the  top  and 
bottom  to  prevent  short-circuiting;  mercury  is  the 
confining  liquid.  The  small  explosion  pipette  holds 

*  Gill,  Am.  Chem.  J.,  14,  231  (1892). 
f  Id.,  J.  Am.  Chem.  Soc.,  18,  67  (1896). 
\  Gill,  J.  Am.  Chem.  Soc.,  17,  771  (1895). 

36 


APPARATUS. 


37 


about  110  cc.  and  is  of  glass,  the  same  thickness  as 
the  simple  pipettes.  Water  is  here  used  as  the  confin- 
ing liquid,  and  also  usually  in  the  burette. 

An  induction  coil  capable  of  giving  a  half-inch  spark, 


FIG.  12.— SHOWING  HEMPEL  BURETTE  CONNECTED  WITH  THE 
SIMPLE  PIPETTE  ON  THE  STAND. 

with   a  six-cell   "Samson"    battery,    four    "simple" 
pipettes  and  a  mercury  burette,  complete  the  outfit. 

The  burette  should  be  carefully  calibrated  and  the 
corrections  may  very  well  be  etched  upon  it  opposite 
the  lO-cc.  divisions. 


38  GAS    AND    FUEL   ANALYSIS. 

In  working  with  the  apparatus  the  pipettes  are  placed 
upon  the  adjustable  stand  5  and  connection  made  with 
the  doubly  bent  capillary  tube. 

Manipulation. — To  acquire  facility  with  the  use  of 
the  apparatus  before  proceeding  to  the  analysis  of 


FIG.  13. — EXPLOSION  PIPETTE  FOR  MERCURY  AND  SULPHURIC 
ACID  PIPETTE. 


illuminating-gas,  it  is  well  to  make  the  following  deter- 
minations, obtaining  "  check  readings  "  in  every  case: 
I.  Oxygen  in  air,  by  (i)  absorption  with  phosphorus 

(2)  absorption  with  potassium  (or  sodium)  pyrogallate 

(3)  by  explosion  with  hydrogen. 


APPARATUS.  39 

I.    DETERMINATION    OF    OXYGEN    IN    AIR. 

(i)  By  Phosphorus. — 100  cc.  of  air  are  measured 
out  as  with  the  Orsat  apparatus,  the  burette  being- 
allowed  to  drain  two  minutes.  The  rubber  connectors 
upon  the  burette  and  pipette  are  filled  with  water,  the 
capillary  tube  inserted,  as  far  as  it  will  go,  by  a  twist- 
ing motion,  into  the  connector  upon  the  burette,  thus 
filling  the  capillary  with  water;  the  free  end  of  the 
capillary  is  inserted  into  the  pipette  connector,  the 
latter  pinched  so  as  to  form  a  channel  for  the  water 
contained  in  it  to  escape,  and  the  capillary  twisted  and 
forced  down  to  the  pinch-cock.  There  should  be  as 
little  free  space  as  possible  between  the  capillaries  and 
the  pinch-cock.  Before  using  a  pipette,  its  connector 
(and  rubber  bag)  should  be  carefully  examined  for 
leaks,  especially  in  the  former,  and  if  any  found  the 
faulty  piece  replaced. 

The  pinch-cocks  on  the  burette  and  pipette  are  now 
opened,  the  air  forced  over  into  the  phosphorus,  and 
the  pinch-cock  on  the  pipette  closed ;  action  im- 
mediately ensues,  shown  by  the  white  fumes ;  after 
allowing  it  to  stand  for  fifteen  minutes  the  residue  is 
drawn  back  into  the  burette,  the  latter  allowed  to  drain 
and  the  reading  taken.  The  absorption  goes  on  best 
at  20°  C.,  not  at  all  at  below  15°  C. ;  it  is  very  much 
retarded  by  small  amounts  of  ethene  and  ammonia. 
No  cognizance  need  be  taken  of  the  fog  of  oxides  of 
phosphorus. 

(2)  By  Pyrogallate  of  Potassium. — 100  cc.  of  air 
are  measured  out  as  before,  the  carbon  dioxide  absorbed 
with  potassium  hydrate  and  the  oxygen  with  potassium 


4O  GAS   AND   FUEL    ANALYSIS. 

pyrogallate,  as  with  the  Orsat  apparatus ;  before  setting 
aside  the  pyrogallate  pipette,  the  number  of  cubic 
centimeters  of  oxygen  absorbed  should  be  noted  upon 
the  slate  s  on  the  stand.  This  must  never  be  omitted 
with  any  pipette  save  possibly  that  for  potassium 
hydrate,  as  failure  to  do  this  may  result  in  the  ruin  of 
an  important  analysis.  The  reason  for  the  omission  in 
this  case  is  found  in  the  large  absorption  capacity — four 
to  five  litres  of  carbon  dioxide — of  the  reagent. 

(3)  By  Explosion  with  Hydrogen. — 43  cc.  of  air 
and  57  cc.  of  hydrogen  are  measured  out,  passed  into 
the  small  explosion  pipette,  the  capillary  of  the  pipette 
filled  with  water,  the  pinch-cocks  and  glass  stop-cock 
all  closed,  a  heavy  glass  or  fine  wire  gauze  screen 
placed  between  the  pipette  and  the  operator,  the  spark 
passed  between  the  spark  wires,  and  the  contraction 
in  volume  noted.  The  screen  should  never  be  omitted, 
as  serious  accidents  may  occur  thereby.  The  oxygen  is 
represented  by  one  third  of  the  contraction.  For  very 
accurate  work  the  sum  of  the  combustible  gases  should 
be  but  one  sixth  that  of  the  non-combustible  gases, 
otherwise  some  nitrogen  will  burn  and  high  results  will 
be  obtained;  *  that  is,  (H  +  O)  :  (N  +  H)  ::  i  :  6. 

II.    ANALYSIS    OF   ILLUMINATING-GAS. 

100  cc.  of  gas  are  measured  from  the  bottle  contain- 
ing the  sample  into  the  burette. 

Determination  of  Carbon  Dioxide. — The  burette 
is  connected  with  the  pipette  containing  potassium 

*  This  is  shown  in  the  work  of  Gill  and  Hunt,  J.  Am.  Chem. 
Soc.,  17,  987  (1895). 


APPARATUS.  41 

hydrate  and  the  gas  passed  into  it  with  shaking  until 
no  further  diminution  in  volume  takes  place. 

Illuminants,  CMH9a ,  CMH3M.e  Series. — The  rubber 
connectors  are  carefully  dried  out  with  filter-paper,  a 
dry  capillary  used,  and  the  gas  passed  into  the  pipette 
containing  fuming  sulphuric  acid  and  allowed  to  stand, 
with  occasional  passes  to  and  fro,  for  forty-five  minutes. 
On  account  of  the  extremely  corrosive  nature  of  the 
absorbent  it  is  not  advisable  to  shake  the  pipette,  as 
in  case  of  breakage  a  serious  accident  might  occur. 
For  Boston  gas  this  is  sufficient,  although  with  richer 
gases  check  readings  to  0.2  cc.  should  be  obtained.^ 
It  is  then  passed  into  potassium  hydrate,  as  in  the 
previous  determination,  to  remove  any  sulphurous  acid 
which  may  have  been  formed  and  any  sulphuric 
anhydride  vapor,  these  having  a  higher  vapor  tension 
than  water.  The  difference  between  this  last  reading 
and  that  after  the  absorption  of  the  carbon  dioxide 
represents  the  volume  of  '  *  illuminants  "  or  "  heavy 
hydrocarbons  ' '  present. 

As  has  already  been  stated,  page  23,  saturated  bromine 
water  may  replace  the  fuming  sulphuric  acid.  Fuming 
nitric  acid  is  not  recommended,  as  it  is  liable  to  oxidize 
carbonic  oxide. 

Oxygen. — This  is  absorbed,  as  in  the  analysis  of 
air,  by  potassium  or  sodium  pyrogallate. 

Carbonic  Oxide. — The  gas  is  now  passed  into  am- 
moniacal  cuprous  chloride,  until  the  reading  is  constant 
to  0.2  cc.  ;  it  is  then  passed  into  a  second  pipette, 
which  is  fresh,  and  absorption  continued  until  constant 
readings  are  obtained. 


42  GAS    AND    FUEL    ANALYSIS. 

Gautier  and  Clausmann  *  have  shown  that  some 
carbonic  oxide  escapes  solution  in  cuprous  chloride,  so 
that  for  very  accurate  work  it  may  be  necessary  to  pass 
the  gas  through  a  U-tube  containing  iodic  anhydride 
heated  to  70°  C. 

This  is  done  by  interposing  this  tube  between  the 
burette  and  a  simple  pipette  filled  with  potassium  hy- 
drate. The  reaction  is  5CO  +  I2O5  =  5CO2  +  2L  The 
diminution  in  volume  represents  directly  the  volume  of 
carbonic  oxide  present. 

The  volume  of  air  contained  in  the  tube  should  be 
corrected  for  as  follows:  One  end  of  the  tube  is  plugged 
tightly  and  the  other  end  connected  with  the  gas  burette 
partly  filled  with  air.  A  bath  of  water  at  9°  C.  is  placed 
around  the  U-tube  and  the  reading  of  the  air  in  the  gas 
burette  recorded  when  constant;  the  bath  is  now  heated 
to  i co°  and  the  burette  reading  again  recorded  when 
constant.  The  increase  in  reading  represents  one  third 
the  volume  of  the  U-tube,  273 1273 +  (100  —  9) :  13:4. 

Methane  and  Hydrogen. — (a)  Hinman's  Method.^ 
— The  gas  left  from  the  absorption  of  carbonic  oxide 
is  passed  into  the  large  explosion  pipette.  About  half 
the  requisite  quantity  of  oxygen  (40  cc.)  necessary 
to  burn  the  gas  is  now  added,  mercury  introduced 
through  the  T  in  the  connector  sufficient  to  seal  the 
capillary  of  the  explosion  pipette,  all  rubber  connectors 
carefully  wired,  the  pinch-cocks  closed,  and  the  pipette 
cautiously  shaken.  A  screen  of  heavy  glass  or  fine 
wire  gauze  is  interposed  between  the  operator  and  the 

*  Bull.  Soc.  Chem.  35,  513;  Abstr.  Analyst,  31,  349  (1906). 
f  Gill  and  Hunt,  J.  Am.  Chem.  Soc.,  17,  987  (1895). 


APPARATUS.  43 

apparatus,  the  explosion  wires  are  connected  with  the 
induction  coil,  a  spark  passed  between  them  and  the 
pinch-cocks  opened,  sucking  in  the  remainder  of  the 
oxygen.  The  capillary  is  again  sealed  with  mercury, 
the  stop-cock  opened  and  closed,  to  bring  the  contents 
of  the  pipette  to  atmospheric  pressure,  and  the  explo- 
sion repeated  as  before,  and  the  stop-cock  opened. 

It  may  be  found  expedient,  to  increase  the  inflamma- 
bility of  the  mixture,  to  inVoduce  5  cc.  of  "  detonating- 
gas,  ' '  the  hydrolytic  mixture  of  hydrogen  and  oxygen. 
The  gas  in  the  pipette  containing  carbon  dioxide, 
oxygen,  and  nitrogen  is  transferred  to  the  mercury 
burette  and  accurately  measured.  The  carbon  dioxide 
resulting  from  the  combustion  of  the  marsh-gas  is 
determined  by  absorption  in  potassium  hydrate ;  to 
show  the  presence  of  an  excess  of  oxygen,  the  amount 
remaining  is  determined  by  absorption  with  potassium 
pyrogallate. 

The  calculation  is  given  on  page  44.  For  very 
accurate  work  a  second  analysis  should  be  made, 
making  successive  explosions,  using  the  percentages  of 
methane  and  hydrogen  just  found  as  a  basis  upon  which 
to  calculate  the  quantity  of  oxygen  to  be  added  each 
time.  The  explosive  mixture  should  be  so  proportioned 
that  the  ratio  of  combustible  gas  (i.e.,  CH4,  H  and  O) 
is  to  the  gases  which  do  not  burn  (i.e.,  N  and  the 
excess  of  CH4  and  H)  as  100  is  to  about  50  (from  26 
to  64);*  otherwise  the  heat  developed  is  so  great  as 
to  produce  oxides  of  nitrogen,  which,  being  absorbed 

*  Bunsen,  Gasometrische  Methoden,  26.  ed.,  p.  73  (1877). 


44  GAS  AND   FUEL   ANALYSIS. 

in  the  potassium  hydrate,  would  affect  the  determina- 
tion of  both  the  methane  and  the  hydrogen.  The 
oxygen  should  preferably  be  pure,  although  commer- 
cial oxygen,  the  purity  of  which  is  known,  can  be 
used ;  the  oxygen  content  of  the  latter  should  be  tested 
from  time  to  time,  especially  with  different  samples. 

(f>)  HempeT  s  Method* — From  12  to  15  cc.  of  the 
gas  are  measured  off  into  the  burette  (e.g.,  13.2  cc.) 
and  the  residue  is  passed  into  the  cuprous  chloride 
pipette  for  safe  keeping.  That  in  the  burette  is  now 
passed  into  the  small  explosion  pipette;  a  volume  of 
air  more  than  sufficient  to  burn  the  gas,  usually  about 
85  cc.,  is  accurately  measured  and  also  passed  into  the 
explosion  pipette,  and  in  so  doing  water  from  the 
burette  is  allowed  to  partially  fill  the  capillary  of  the 
pipette  and  act  as  a  seal.  The  rubber  connectors  upon 
the  capillaries  of  the  burette  and  pipette  are  carefully 
wired  on,  both  pinch-cocks  shut,  and  the  stop-cock 
closed.  The  pipette  is  cautiously  shaken,  the  screen 
interposed,  the  explosion  wires  connected  with  the 
induction  coil,  a  spark  passed  between  them,  and  the 
stop-cock  immediately  opened.  The  gas  in  the  pipette, 
containing  carbon  dioxide,  oxygen,  and  nitrogen,  is 
transferred  to  the  burette,  accurately  measured,  by 
reading  immediately,  to  prevent  the  absorption  of  car- 
bon dioxide,  and  carbon  dioxide  and  oxygen  deter- 
mined in  the  usual  way. 

Calculation. — (a)  Hinman's  Method. — 56.2  cc.  of 
gas  remained  after  the  absorptions;  77.4  cc.  of  oxygen 
were  introduced,  giving  a  total  volume  of  133.6  cc. 

*  Hempel,  Gas  Analytische  Methodcn,  3d  ed.,  p.  245  (1901). 


APPARATUS. 


45 


Residue  after  explosion 46.9  cc. 

Residue  after  COa  absorption 28.2    " 

Carbon  dioxide  formed 18.7    " 

Contraction 133.6  —  46.9=  86.7    " 

Residue  after  O  absorption 25.6    " 

Oxygen   in   excess,  28.2  —  25.6  =  2.6   " 

The  explosion  of   marsh-gas  or  methane  is  repre- 
sented by  the  equation* 


CH4 


O, 


o. 


=     CO, 


+ 


H20 


From  this  it  is  evident  that  the  volume  of  carbon 
dioxide  is  equal  to  the  volume  of  methane  present; 
therefore  in  the  above  example,  in  the  56.2  cc.  of  gas 
burned  there  were  18.7  cc.  methane. 

The  total  contraction  is  due  (i)  to  the  disappearance 
of  oxygen  in  combining  with  the  hydrogen  of  the 
methane,  and  (2)  to  the  union  of  the  free  hydrogen 
with  oxygen.  The  volume  of  the  methane  having 
been  found,  (i)  can  be  ascertained  from  the  equation 
above,  equals  twice  the  volume  of  the  methane;  hence 

86.7  —  (2  X  18.7)  =-49.3  cc., 

contraction  which  is  due  to  the  combustion  of  hydrogen* 
This  takes  place  according  to  the  following  reaction:  * 


H, 


O,     = 


H..O 


H.O 


*  H2O  being  as   steam    at    100°  C.     At  ordinary  temperatures 
this  is  condensed,  giving  rise  to  "  total  contraction." 


46  -GAS  AND    FUEL  ANALYSIS. 

Hydrogen  then  requires  for  its  combustion  half  its 
volume  of  oxygen,  hence  this  49.3  cc.  represents  a 
volume  of  hydrogen  with  \  its  volume  of  oxygen,  or 
|  volumes;  hence  the  volume  of  hydrogen  is  32.9  cc. 

(<£)  Hemper s  Method. — Of  the  82  cc.  of  gas  remain- 
ing after  the  absorptions,  13.2  cc.  were  used  for  the 
explosion ;  86.4  cc.  air  introduced  giving  a  total  volume 
of  99.6  cc. 

Residue  after  explosion 78.0  cc. 

Residue  after  CO2  absorption 73 .2    " 


Carbon  dioxide  formed 4.8  4< 

Contraction 99.6  —  78.0=  21.6  " 

Residue  after  O  absorption 70.2  " 

Oxygen  in  excess.  .73.2  —  70.2  =  3.0  " 

The  carbon  dioxide  being  equal  to  the  methane 
present,  in  the  13.2  cc.  of  gas  burned,  there  were 
4.8  cc.  of  methane.  The  volume  of  methane  is  found 
by  the  proportion  13.2  :  82  : :  4.8  :  x,  whence  x  — 
29.8  cc. 

The  hydrogen  is  calculated  similarly. 

The  following  method  of  calculation  may  be  substi- 
tuted for  that  on  page  43 :  Let  m  =  methane,  h  = 
hydrogen,  c  =  total  contraction,  and  O  —  oxygen 
actually  used ;  then 


and 


+       =  c, 


APPARA  TVS.  47 

whence 

3O  —  c 

^T 

and 

h  =  c  -  O. 

The  explosion  can  also  be  made  after  the  absorption 
of  oxygen  and  thus  the  troublesome  absorption  of  car- 
bonic oxide  avoided.  The  calculation  is  then,  if  C  — 
carbonic  oxide,  K  =  COa  formed  : 


2     ' 

K  =  C  - 

2 

\  / 

(2) 

I             it,. 

h  m  +  n>       •     • 

.     •     (3) 

whence 

h  =  V  -  K, 


2K  2C 

m  =  ---  V  A  --  . 
3  3 

Another  method  for  the  estimation  of  hydrogen  is 
by  absorption  with  palladium  sponge  ;  *  it,  however, 
must  be  carefully  prepared,  and  it  is  the  author's 
experience  that  one  cannot  be  sure  of  its  efficacy  when 
it  is  desired  to  make  use  of  it.  A  still  better  absorbent 
of  hydrogen  t  is  a  I  per  cent  solution  of  palladous 

*  Hempel,  Berichte  deutsch.  ch.  Gesell.,  12,  636  and  1006(1879). 
\  Campbell  and  Hart,  Am.  Chem.  J.,  18,  294  (1896). 


48  GAS  AND   FUEL   ANALYSIS. 

chloride  at  50°  C.  ;  when  fresh  this  will  absorb  20-50 
cc.  of  hydrogen  in  ninety  minutes.  A  proportionately 
longer  time  is  required  if  more  hydrogen  be  present  or 
the  solution  nearly  saturated.  The  methane  could 
then  be  determined  by  explosion  or  by  mixing  with 
air  and  passing  to  and  fro  over  a  white-hot  platinum 
spiral  in  a  tubulated  pipette  called  the  grisoumeter  * 
(grisou  =  methane). 

Nitrogen. — There  being  no  direct  and  convenient 
method  for  its  estimation  with  this  apparatus,  the  per- 
centage is  obtained  by  finding  the  difference  between 
the  sum  of  all  the  percentages  of  the  gases  determined 
and  100  per  cent. 

New  f  determines  nitrogen  in  illuminating-gas  di- 
rectly after  the  method  of  Dumas  in  organic  sub- 
stances; 150  cc.  of  gas  are  used,  the  hydrocarbons 
partially  absorbed  by  fuming  sulphuric  acid  and  the 
remainder  burned  in  a  combustion  tube  with  copper 
oxide ;  the  carbon  dioxide  is  absorbed  and  the  residual 
nitrogen  collected  and  measured. 

Accuracy  and  Time  Required. — For  the  absorp- 
tions the  apparatus  is  accurate  to  o.  I  cc.  ;  for  explosions 
by  Hinman's  method  '\.  the  methane  can  be  determined 
within  0.2  per  cent,  the  hydrogen  within  0.3  per  cent; 
by  Hempel's  method  within  I  per  cent  for  the  methane 
and  7.5  per  cent  for  the  hydrogen.  The  time  required 
for  the  analysis  of  illuminating-gas  is  from  three  to 
three  and  one-half  hours ;  for  air,  from  fifteen  to  twenty 
minutes. 

*  Winkler,  Fres.  Zeit.,  28,  269  and  288. 
f  J.  Soc.  Chem.  Ind.,  II,  415  (1892)0 
\  Gill  and  Hunt,  loc  cit. 


APPARA  TVS.  49 

Notes. — The  object  in  filling  the  capillaries  of  the 
explosion  pipettes  with  water  or  mercury  before  the 
explosion  is  to  prevent  the  bursting  of  the  rubber  con- 
nectors on  them.  With  mercury  this  is  effected  by 
introducing  it  through  the  T  joint  in  the  connector. 
After  testing  for  oxygen  with  the  pyrogallate  a  small 
quantity  of  dilute  acetic  acid  is  sucked  into  the  burette 
to  neutralize  any  alkali  which  by  any  chance  may  have 
been  sucked  over  into  it.  The  acid  is  rinsed  out  with 
water  and  this  forced  out  by  mercury  before  the  burette 
is  used  again. 

The  water  in  the  burette  should  be  saturated  with 
the  gas  which  is  to  be  analyzed — as  illuminating-gas 
— before  beginning  an  analysis.  The  reagents  in  the 
pipettes  should  also  be  saturated  with  the  gases  for 
which  they  are  not  the  reagent.  For  example,  the 
fuming  sulphuric  acid  should  be  saturated  with  oxygen, 
carbon  monoxide,  methane,  hydrogen,  and  nitrogen; 
this  is  effected  by  making  a  blank  analysis  using 
illuminating-gas. 

The  method  of  analysis  of  the  residue  after  the 
absorptions  have  been  made  by  explosion  is  open  to 
two  objections:  1st,  the  danger  of  burning  nitrogen  by 
the  violence  of  the  explosion;  and  2d,  the  danger  of 
breakage  of  the  apparatus  and  possible  injury  to  the 
operator.  These  may  be  obviated  by  employing  the 
apparatus  of  Dennis  and  Hopkins, *  which  is  practically 
a  grisoumeter  with  mercury  as  the  confining  liquid ;  or 
that  of  Jager,  t  who  burns  the  gases  with  oxygen  in  a 

*  J.  Am.  Chern.  Soc.,  21,  398  (1899). 

f  J.  f.  Gasbeleuchtung,  41,  764.  Abstr.  J.  Soc.  Chem.  Ind., 
17,  1190  (1898). 


50  CAS   AND    FUEL   ANALYSIS. 

hard-glass  tube  filled  with  copper  oxide.  By  heating 
to  250°  C.  nothing  but  hydrogen  is  burned;  higher 
heating  of  the  residue  burns  the  methane.  Or  the  mix- 
ture of  oxygen  and  combustible  gases,  bearing  in  mind 
the  ratio  mentioned  at  the  bottom  of  page  43,-  can  be 
passed  to  and  fro  through  Drehschmidt's  *  capillary 
heated  to  bright  redness.  This  consists  of  a  platinum 
tube  20  cm.  long,  2  mm.  thick,  1.7  mm.  bore,  filled  with 
three  platinum  or  palladium  wires.  The  ends  of  the  tube 
are  soldered  to  capillary  brass  tubes  and  arranged  so 
that  these  can  be  water  cooled.  It  is  inserted  between 
the  burette  and  a  simple  pipette,  mercury  being  the  con- 
fining liquid  in  both  cases.  The  air  contained  in  the 
tube  can  be  determined  as  in  the  case  of  the  tube  contain- 
ing iodic  anhydride,  p.  42. 

To  the  method  of  explosion  by  the  mixture  of  an 
aliquot  part  of  the  residue  with  air,  method  (b),  there 
is  the  objection  that  the  carbon  dioxide  formed  is  meas- 
ured over  water  in  a  moist  burette,  giving  abundant 
opportunities  for  its  absorption,  and  that  the  errors  in 
anylysis  are  multiplied  by  about  six,  in  the  example 

by  m 

*  Ber.  d.  dent.  chem.  Gesell.  21,  3242  (1888). 


CHAPTER    VI. 

REAGENTS  AND  ARRANGEMENT  OF  THE 
LABORATORY. 

THE  reagents  used  in  gas-analysis  are  comparatively 
few  and  easily  prepared. 

Hydrochloric  Acid,  Sp.  gr.  i.io. — Dilute  "muri- 
atic acid  "  with  an  equal  volume  of  water.  In  addi- 
tion to  its  use  for  preparing  cuprous  chloride,  it  finds 
employment  in  neutralizing  the  caustic  solutions  which 
are  unavoidably  more  or  less  spilled  during  their  use. 

Fuming  Sulphuric  Acid. — Saturate  "  Nordhausen 
oil  of  vitriol"  with  sulphuric  anhydride.  Ordinary 
sulphuric  acid  may  be  used  instead  of  the  Nordhausen  ; 
in  this  case  about  an  equal  weight  of  sulphuric  an- 
hydride will  be  necessary.  Absorption  capacity ',  I  cc. 
absorbs  8  cc.  of  ethene  (ethylene). 

Acid  Cuprous  Chloride. — The  directions  given  in 
the  various  text-books  being  troublesome  to  execute, 
the  following  method,  which  is  simpler,  has  been 
found  to  give  equally  good  results.  Cover  the  bottom 
of  a  two-liter  bottle  with  a  layer  of  copper  oxide  or 
"  scale  "|  in.  deep,  place  in  the  bottle  a  number  of 
pieces  of  rather  stout  copper  wire  reaching  from  top 
to  bottom,  sufficient  to  make  a  bundle  an  inch  in 
diameter,  and  fill  the  bottle  with  common  hydrochloric 

5* 


52  GAS  AND    FUEL   ANALYSIS. 

acid  of  1 . 10  sp.  gr.  The  bottle  is  occasionally  shaken, 
and  when  the  solution  is  colorless,  or  nearly  so,  it  is 
poured  into  the  half-liter  reagent  bottles,  containing 
copper  wire,  ready  for  use.  The  space  left  in  the 
stock  bottle  should  be  immediately  filled  with  hydro- 
chloric acid  (i.io  sp.  gr.). 

By  thus  adding  acid  or  copper  wire  and  copper 
oxide  when  either  is  exhausted,  a  constant  supply  of 
this  reagent  may  be  kept  on  hand. 

The  absorption  capacity  of  the  reagent  per  cc.  is, 
according  to  Winkler,  15  cc.  CO;  according  to 
Hempel  4  cc.  The  author's  experience  with  Orsat's 
apparatus  gave  I  cc. 

Care  should  be  taken  that  the  copper  wire  does  not 
become  entirely  dissolved  and  that  it  extend  from  the 
top  to  the  bottom  of  the  bottle;  furthermore  the 
stopper  should  be  kept  thoroughly  greased  the  more 
effectually  to  keep  oat  the  air,  which  turns  the  solution 
brown  and  weakens  it. 

Ammoniacal  Cuprous  Chloride. — The  acid  cu- 
prous chloride  is  treated  with  ammonia  until  a  faint 
odor  of  ammonia  is  perceptible;  copper  wire  should 
be  kept  in  it  similarly  to  the  acid  solution.  This 
alkaline  solution  has  the  advantage  that  it  can  be 
used  when  traces  of  hydrochloric  acid  vapors  might 
be  harmful  to  the  subsequent  determinations,  as,  for 
example,  in  the  determination  of  hydrogen  by  absorp- 
tion with  palladium.  It  has  the  further  advantage 
of  not  soiling  mercury  as  does  the  acid  reagent. 

Absorption  capacity,  I  cc.  absorbs  I  cc.  CO. 

Cuprous  chloride  is  at  best  a  poor  reagent  for  the 
absorption  of  carbonic  oxide;  to  obtain  the  greatest 


REAGENTS  AND    LABORATORY.  53 

accuracy  where  the  reagent  has  been  much  used,  the 
gas  should  be  passed  into  a  fresh  pipette  for  final 
absorption,  and  the  operation  continued  until  two 
consecutive  readings  agree  exactly.  The  compound 
formed  by  the  absorption — possibly  Cu2COCl2 — is  very 
unstable,  as  carbonic  oxide  may  be  freed  from  the 
solution  by  boiling  or  placing  it  in  vacuo ;  even  if  it 
be  shaken  up  with  air,  the  gas  is  given  off,  as  shown 
by  the  increase  in  volume  and  subsequent  diminution 
when  shaken  with  fresh  cuprous  chloride. 

Hydrogen. — A  simple  and  effective  hydrogen  gen- 
erator can  be  made  by  joining  two  six-inch  calcium 
chloride  jars  by  their  tubulatures.  Pure  zinc  is  filled 
in  as  far  as  the  constriction  in  one,  and  the  mouth 
closed  with  a  rubber  stopper  carrying  a  capillary  tube 
and  a  pinch-cock.  The  other  jar  is  filled  with 
sulphuric  acid  I  :  5  which  has  been  boiled  and  cooled 
out  of  access  of  air.  The  mouth  of  this  jar  is  closed 
with  a  rubber  stopper  carrying  one  of  the  rubber  bags 
used  on  the  simple  pipettes. 

Mercury. — The  mercury  used  in  gas  analysis  should 
be  of  sufficient  purity  as  not  to  "drag  a  tail"  when 
poured  out  'rom  a  clean  vessel.  It  may  perhaps  be 
most  conveniently  cleaned  by  the  method  of  J.  M. 
Crafts,  which  consists  in  drawing  a  moderate  stream 
of  air  through  the  mercury  contained  in  a  tube  about 
3  feet  long  and  li  inches  internal  diameter.  The  tube 
is  supported  in  a  mercury-tight  V-shaped  trough,  of 
size  sufficient  to  contain  the  metal  if  the  tube  breaks, 
one  end  being  about  3  inches  higher  than  the  other. 
Forty-eight  hours'  passage  of  air  is  sufficient  to  purify 
any  ordinary  amalgam.  The  mercury  may  very  well 


54  GAS  AND    FUEL   ANALYSIS. 

be  kept  in  a  large  separatory  funnel  under  a  layer  of 
strong  sulphuric  acid. 

Fallacious  Chloride. — 5  grams  palladium  wire  are  dis- 
solved in  a  mixture  of  30  cc.  hydrochloric  and  2  cc.  nitric 
acid,  this  evaporated  just  to  dryness  on  a  water-bath,  re- 
dissolved  in  5  cc.  hydrochloric  acid  and  2  5  cc.  water,  and 
warmed  until  solution  is  complete.  It  is  diluted  to  750  cc. 
and  contains  about  one  per  cent  of  palladous  chloride.  It 
will  absorb  about  two  thirds  of  its  volume  of  hydrogen. 

Phosphorus. — Use  the  ordinary  white  phosphorus 
cast  in  sticks  of  a  size  suitable  to  pass  through  the 
opening  of  the  tubulated  pipette. 

Potassium  Hydrate. — (a)  For  carbon  dioxide  de- 
termination, 500  grams  of  the  commercial  hydrate  is 
dissolved  in  I  liter  of  water. 

Absorption  capacity,  i  cc.  absorbs  40  cc.  CO2. 

(b)  For  the  preparation  of  potassium  pyrogallatc 
for  special  work,  120  grams  of  the  commercial  hydrate 
is  dissolved  in  100  cc.  of  water. 

Potassium  Pyrogallate. — Except  for  use  with  the 
Orsat  or  Hempel  apparatus,  this  solution  should  be 
prepared  only  when  wanted.  The  most  convenient 
method  is  to  weigh  out  5  grams  of  the  solid  acid  upon 
a  paper,  pour  it  into  a  funnel  inserted  in  the  reagent 
bottle,  and  pour  upon  it  loocc.  of  potassium  hydrate 
(a)  or  (b).  The  acid  dissolves  at  once,  and  the  solution 
is  ready  for  use. 

If  the  percentage  of  oxygen  in  the  mixture  does 
not  exceed  28,  solution  (a)  may  be  used;*  if  this 
amount  be  exceeded,  (b)  must  be  employed.  Other- 
wise carbonic  oxide  may  be  given  off  even  to  the 
extent  of  6  per  cent. 

*  Clowes,  Jour.  Soc,  Chem.  Industry,  15,  170. 


REAGENTS  AND    LABORATORY.  55 

Attention  is  called  to  the  fact  that  the  use  of  potas- 
sium hydrate  purified  by  alcohol  has  given  rise  to 
erroneous  results. 

Absorption  capacity,  I  cc.  absorbs  2  cc.  O.. 

Sodium  Hydrate. — Dissolve  the  commercial  hy- 
drate in  three  times  its  weight  of  water.  This  may  be 
employed  in  all  cases  where  solution  (a)  of  potassium 
hydrate  is  used.  The  chief  advantage  in  its  use  is  its 
cheapness,  it  costing  but  one  tenth  as  much  as  potas- 
sium hydrate,  a  point  to  be  considered  where  large 
classes  are  instructed.  Sodium  pyrogallate  is,  how- 
ever, a  trifle  slower  in  action  than  the  corresponding 
potassium  salt. 

ARRANGEMENT   OF   THE   LABORATORY. 

The  room  selected  for  a  laboratory  for  gas-analysis 
should  be  well  lighted,  preferably  from  the  north  and 
east.  To  prevent  changes  in  temperature  it  should 
be  provided  with  double  windows,  and  the  method  of 
heating  should  be  that  which  will  give  as  equable  a 
temperature  as  possible.  In  the  author's  laboratory, 
instead  of  the  usual  tables,  shelves  are  used,  18  inches 
wide  and  ij  inches  thick,  best  of  slate  or  soapstone, 
firmly  fastenec.  to  the  walls,  30  inches  from  the  floor; 
the  Orsat  apparatus,  when  not  in  use,  may  be  sus- 
pended from  these.  The  reagents  are  contained  in 
half-liter  bottles  fitted  with  rubber  stoppers,  placed 
upon  a  central  table  convenient  to  all.  Here  are 
found  scales,  funnels  and  graduates  for  use  in  making 
up  reagents.  Distilled  water  is  piped  around  to  each 
place  by  -J-inch  tin  pipe  and  T3F-inch  rubber  tubing 
from  a  j-inch  "main,"  being  supplied  at  the  tern- 


56  GAS  AND    FUEL    ANALYSIS. 

perature  of  the  room  from  bottles  placed  about  six 
feet  above  the  laboratory  shelves.  A  supply  of  a 
gallon  per  day  per  student  should  be  provided. 

At  the  right  of  each  place  is  fixed  a  sand-glass  of 
cylindrical  rather  than  conical  form,  graduated  to 
minutes  for  the  draining  of  the  burettes.  The  "egg- 
timers  "  found  in  kitchen-furnishing  stores  serve  the 
purpose  admirably. 

"  Unknown  gases  "  for  analysis  are  best  contained 
in  a  Muencke  double  aspirator,  Fig.  14,  where  they 


FIG.  14. — MUENCKE'S  ASPIRATOR. 

can  be  thoroughly  mixed  before  distribution  and  con- 
veyed by  a  pipe  to  the  central  table. 

Finally,  the  laboratory  should  contain  a  stone-ware 
sink    provided    with    an    efficient    trap    of    the   same 


REAGENTS  AND    LABORATORY.  $, 

material,  to  prevent  mercury  from  being  carried  into 
and  corroding  the  lead  waste-pipes. 

Drawers  should  be  provided  with  compartments  for 
various  sizes  of  rubber  connectors,  pinchcocks,  glass 
tubing,  stoppers  and  fittings,  and  tools.  When  work- 
ing with  the  Orsat  apparatus  alone,  three  feet  of  shelf 
space  may  be  allowed  to  each  student;  when  using  this 
with  another,  as,  for  example,  the  Bunte,  another 
foot  should  be  added. 

The  course  which  the  writer  has  been  in  the  habit 
of  giving  to  the  Mechanical  and  Electrical  Engineers 
embraces  two  exercises  in  the  laboratory  of  two  hours 
each,  supplemented  with  four  hours  of  lectures.  The 
students  in  the  laboratory  make  an  analysis  of  air  and 
an  "unknown"  furnace-gas,  take  and  analyze  an 
actual  sample  of  chimney-gas,  and  make  the  calculation 
of  heat  lost  and  air  used.  In  the  lectures,  the  subject 
of  gas-analysis  and  its  other  applications,  and  of  fuels, 
their  origin,  description,  preparation,  analysis,  and 
determination  of  heating  value,  are  described. 


CHAPTER    VII. 

FUELS— SOLID,   LIQUID,  AND  GASEOUS:  THEIR 
DERIVATION   AND   COMPOSITION. 

The  substances  employed  as  fuels  are: 

a.  SOLID  FUELS. — Wood,  peat,  brown,  bituminous 
and   anthracite  coal,   charcoal,    coke,   and   oftentimes 
various   waste  products,  as  sawdust,    bagasse,   straw, 
and  spent  tan. 

b.  LIQUID   FUELS. — Crude  petroleum  and  various 
tarry  residues. 

c.  GASEOUS  FUELS. — Natural  gas,  producer,     blast- 
furnace, water,  and  illuminating  gas. 

The  essential  constituents  in  all  these  are  carbon  and 
hydrogen;  the  accessory,  oxygen,  nitrogen,  and  ash; 
and  the  deleterious,  water,  sulphur,  and  phosphorus. 

a.  SOLID  FUELS. 

Wood  is  composed  of  three  substances — cellulose, 
or  woody  fibre  (C9H10O6)M  ;  the  components  of  the  sap, 
the  chief  of  which  is  lignine,  a  resinous  substance  of 
identical  formula  with  cellulose;  and  water.  The 
formation  of  cellulose  from  carbon  dioxide  and  water 
may  be  represented  by  the  equation 

6CO,  +  5H,0  =  C.H100.  +  60,. 

The  amount  of  water  which  wood  contains  determines 
its  value  as  a  fuel.     This  varies  from  29  per  cent  in  ash 

58 


FUELS— SOLID,  LIQUID,  AND  GASEOUS.  59 

to  50  per  cent  in  poplar;  it  varies  also  with  the  season 
at  which  the  wood  is  cut,  being  least  when  the  sap  is  in 
the  roots — in  December  and  January.  This  difference 
may  amount  to  10  per  cent  in  the  same  kind  of  wood. 

The  harder  varieties  of  wood  make  the  best  fuel,  a 
cord  of  seasoned  hardwood  being  about  equal  to  a  ton 
of  coal.  Yellow  pine,  however,  has  but  half  this 
value;  the  usual  allowance  in  a  boiler-test  is  0.4  the 
value  of  an  equ^l  weight  of  coal. 

The  ash  of  wood  is  mainly  potassium  carbonate, 
with  traces  of  other  commonly  occurring  substances, 
as  lime,  magnesia,  iron,  silica,  and  phosphoric  acid. 

The  percentage  composition  of  wood  may  be  con- 
sidered as  approximately, 

Water.        Carbon.        Hydrogen.        Oxygen.          Ash.  Sp.  Gr. 

20  39  4.4  35.6  I  0.5.* 

When  burned  it  yields  about  4000  C.  per  kilo,  and 
requires  6  times  its  weight  of  air  or  4.6  cu.  m.  (74.1 
cu.  ft.  per  pound)  for  its  combustion. 

Peat  finds  considerable  application  in  Europe,  and 
is  coming  into  use  in  this  country  in  the  form  of  bri- 
quettes. To  this  end  it  is  reduced  to  a  dry  powder 
and  compresseu  into  small  cylindrical  blocks;  it  is 
claimed  to  be  as  efficient  as  coal  at  half  the  price.  It 
is  also  proposed  to  gasify  peat  after  the  manner  of 
coal.  Peat  is  produced  by  the  slow  decay  underwater 
o(  certain  swamp  plants,  more  especially  the  mosses 
(Sphagnaceae),  evolving  methane  (CH4)  (marsh-gas) 
and  carbon  dioxide  (CO,). 

It  contains  considerable  moisture,  from  20  to  50 
per  cent,  and  10  per  cent  even  when  "thoroughly 
*  Mills  &  Rowan,  Fuels,  p.  n. 


60  GAS  AND    FUEL   ANALYSIS. 

dry."  Thirty  per  cent  of  its  available  heat  is  employed 
in  evaporating  this  moisture.  The  high  content  of 
ash,  from  3  to  30  per  cent,  averaging  15  per  cent,  also 
diminishes  its  value  as  a  fuel. 

The  ash  of  peat  differs  from  that  of  wood  in  contain- 
ing little  or  no  potassium  carbonate. 

The  percentage  composition  of  peat  may  be  consid' 
ered  as  approximately, 

Water.      Carbon.  Hydrogen.  Oxygen.  Nitrogen.     Ash.       Sp.  Gr- 
German....    16.4         41.0         4.3          23.8        2.6         11.9       1.05 

American...    20.8         40.8         4.4  26.6  7.7        — 

Such  peat  is  about  equivalent  to  wood  in  its  heating 
effect,  one  pound  evaporating  from  4.5  to  5  pounds 
of  water. 

Coal.  —  Geologists  tell  us  that  coal  was  probably 
produced  by  the  decay  under  fresh  water  of  plants 
belonging  principally  to  the  Conifer,  Fern  and  Palm 
families;  these  flourished  during  the  Carboniferous 
Age  to  an  extent  which  they  never  approached  before 
or  since.  Representatives  of  the  last  family,  which 
it  is  thought  produced  most  of  the  coal,  have  been 
found  2  to  4  feet  in  diameter  and  80  feet  in  height. 

By  their  decay,  carbon  dioxide  "  choke-damp," 
marsh-gas  "  fire-damp,"  and  water  were  evolved. 
The  change  might  be  represented  by  the  equation 


6C.HM  O.  -  7CO,  +  3CH.+ 

Cellulose.  Bituminous  Coal. 

Some  idea  of  the  density  of  the  vegetation  and  the 
time  required  may  be  obtained  from  the  fact  that  it 
has  been  calculated  that  100  tons  of  vegetable  matter 
—  the  amount  produced  per  acre  per  century  —  if  com- 
pressed to  the  specific  gravity  of  coal  and  spread  over 


FUELS— SOLID,  LIQUID,  AND    GASEOUS.  6 1 

an  acre  would  give  a  layer  less  than  0.6  of  an  inch 
thick.  Now  four  fifths  of  this  is  lost  in  the  evolution 
of  the  gaseous  products,  giving  as  a  result  an  accumu- 
lation of  one  eighth  of  an  inch  per  century,  or  one  foot 
in  io,OOO  years.* 

Brown  Coal  or  Lignite  may  be  regarded  as  forming 
the  link  between  wood  and  coal ;  geologically  speaking 
it  is  of  later  date  than  the  true  coal.  Most  of  the  coal 
west  of  the  Rocky  Mountains  is  of  this  variety. 

As  its  name  denotes,  it  generally  is  of  brown  color 
— although  the  western  coal  is  black — and  has  a  con- 
choidal  fracture.  It  contains  a  large  quantity  of 
water  when  first  mined,  as  much  as  60  per  cent,  and 
when-"  air-dry"  from  15  to  20  per  cent.  The  per 
cent  of  ash  is  also  high,  from  I  to  20  per  cent. 

The  average  moisture  and  ash  in  American  lignites 
are  12.75  an<^  6.1  respectively. 

The  percentage  composition  of  brown  coal  may  be 
considered  as  approximately, 

Water.  Carbon.         Hydrogen.  Oxygen  &  Nitrogen.   Ash.  Sp.  Gr. 

German     18.0  50.9  4.6  16.3  10.2  1.3 

Bituminous  Coal. — This  is  the  variety  from  which  all 
the  following  coals  are  supposed  to  have  been  formed, 
by  a  process  of  natural  distillation  combined  with  pres- 
sure. According  to  the  completeness  of  this  process 
we  have  specimens  which  contain  widely  differing  quan- 
tities of  volatile  matter.  This  forms  the  true  basis  for 
the  distinguishing  of  the  varieties  of  coal.  In  ordinary 
bituminous  coal  this  volatile  matter  amounts  to  30  or 
40  per  cent.  Three  varieties  of  bituminous  coal  are 
ordinarily  distinguished,  as  follows: 

*  In  case  the  student  desires  to  follow  in  a  more  extended 
manner  the  geology  of  coal,  reference  may  be  had  to  Le  Conte's 
"  Elements  of  Geology."  nr>.  ^c_4I4)  3d  ed. 


62  GAS  AND   FUEL   ANALYSIS. 

Dry  or  non-caking  —those  which  burn  freely  with  but 
little  smoke  and — as  the  name  denotes — do  not  cake 
together  when  burned.  The  coals  from  Wyoming 
are  an  example  of  this  class. 

Caking — those  which  produce  some  smoke  and  cake 
or  sinter  together  in  the  furnace.  An  example  of 
these  is  the  New  River  and  Connellsville  coal. 

Fat  or  Long-flaming — those  producing  much  flame 
and  smoke  and  do  or  do  not  cake  in  burning;  volatile 
matter  50  per  cent  or  more.  Some  of  the  Nova 
Scotia  coals  belong  to  this  class. 

Bituminous  coal  varies  much  in  its  composition — is 
black  or  brownish  black,  soft,  friable,  lustrous,  and  of 
specific  gravity  of  1.25  to  1.5. 

Moisture  varies  from  0.25  to  8  per  cent,  averaging 
about  5. 

The  percentage  composition  of  bituminous  coal  may 
be  considered  as  approximately,* 

Water.  Carbon.        Hydrogen.  Oxygen.      Nitrogen  Ash.           Sulphur. 

0.9  77.1              5.2  0.7             1.6  7.6             i.o 

Water.  Volatile  Matter.  Fixed  Carbon.  Ash. 

0.9  27.4  64.1  7.6 

Semi-Biturninous  or  Semi-Anthracite  Coal  is  upon  the 
border-line  between  the  preceding  and  the  following 
variety;  it  is  harder  or  softer  than  bituminous,  contains 
less  volatile  matter  (15  to  20  per  cent),  and  burns 
with  a  shorter  flame.  An  example  of  this  is  the 
Pocahontas  coal. 

The  percentage  composition  of  semi- bituminous  and 
semi-anthracite  coal  may  be  considered  to  be  approxi- 
mately,* 

Water.          Carbon.         Hydrogen.      Oxygen.       Nitrogen.         Ash.  Sulphur. 

0.5  83.0  4.7  4.2  1.3  5.5  0.8 

Water.  Volatile  Matter.  Fixed  Carbon.  Ash. 

Q.5 16.7  77.3 5-5 

*  H.  J.  Williams. 


FUELS— SOLID,  LIQUID,  AND    GASEOUS.  63 

Anthracite  Coal  is  the  hardest,  most  lustrous,  and 
densest  of  all  the  varieties  of  coal,  having  a  specific 
gravity  of  1.3  to  1.75;  it  contains  the  most  carbon 
and  least  hydrogen  and  volatile  matter  (5  to  10  per 
cent).  It  has  a  vitreous  fracture  and  kindles  with 
difficulty,  burning  with  a  feeble  flame,  giving  little  or 
no  smoke  and,  with  sufficient  draft,  an  intense  fire. 
The  Lehigh  coal  is  an  excellent  example  of  this  class. 

The  percentage  composition  of  anthracite  coal  may 
be  considered  as  approximately,* 

Water.          Carbon.       Hydrogen.     Oxygen.     Nitrogen.         Ash.          Sulphur. 
2.0  83.9  2.7  2.8  0.8  7.2  0.6 

Water.  Volatile  Matter.  Fixed  Carbon.  Ash. 

2.0  4.3  86.5  7.2 

The  ash  of  coal  varies  from  I  to  20  per  cent 
and  is  mainly  clay — silicate  of  alumina- — with  lime, 
magnesia,  and  iron.  When  coal  is  burned  it  yields 
from  6100  to  8000  C.  and  requires  about  12  times  its 
weight  of  air,  9.76  cu.  m.  per  kilo  or  156.7  feet  per 
pound.  For  the  greatest  economy  Scheurer-Kestner  f 
found  that  this  should  be  increased  from  50  to  100 
per  cent. 

Charcoal  is  prepared  by  the  distillation  or  smoulder- 
ing of  wood,  either  in  retorts,  where  the  valuable 
by-products  are  saved,  or  in  heaps.  It  should  be 
jet-black,  of  bright  lustre  and  conchoidal  fracture. 

When  wood  is  charred  in  heaps  only  about  20  per 
cent  of  its  weight  in  charcoal  is  obtained — 48  bushels 
per  cord,  or  about  half  the  percentage  of  carbon. 
When  retorts  or  kilns  are  employed,  the  yield  is  in- 
creased to  30  per  cent,  and  40  per  cent  of  pyroligneous 

*H.  J.  Williams. 

j  Jour.  Soc.  Chem.  Industry,  7,  616. 


64  GAS  AND    FUEL   ANALYSIS. 

acid   of    10  per  cent  strength,  with  4  per  cent  of  tar, 
are  obtained. 

The  percentage  composition  of  wood-charcoal  may  be 
considered  as  approximately, 

Carbon.  Ash.  Sp.  Gr. 

97.O  3.0  O.2 

Coke  is  prepared  by  the  distillation  of  bituminous 
coal  in  ovens;  these  are  of  two  types,  those  in  which 
the  distillation-products  are  allowed  to  escape — the 
"'beehive  "  ovens — and  those  in  which  they  are  care- 
fully saved,  as  the  Otto-Hoffman,  Semet-Solvay, 
Simon-Carves',  and  others. 

The  "beehive"  ovens  yield  from  50  to  65  per 
cent  of  the  weight  of  the  coal — about  2^  tons.  The 
Otto-Hoffman  ovens  are  long  narrow  thin-walled  re- 
torts 33  by  6  by  1.5  feet,*  regeneratively  heated  by  side 
and  bottom  flues;  the  charge  is  about  6  tons  of  coal, 
and  the  following  percentage  yields  of  by-products 
are  obtained:  coke  70-75,  gas  16  (10  M.  cu.  ft.),  tar 
3.3-5.6,  ammonia  0.3-1.44  The  Semet-Solvay  ovens 
differ  from  the  above  in  that  they  are  not  regen- 
eratively heated  and  their  walls  are  thicker,  serving  to 
store  up  the  heat;  the  yield  of  coke  is  somewhat 
m'gher — about  80  per  cent.J  The  by-products  ob- 
tained alone  increase  the  value  of  the  output  about 
one  and  one  half  times.  Good  coke  should  possess  a 
cellular  structure,  a  metallic  ring,  contain  practically 
no  impurities,  and  be  capable  of  bearing  a  heavy 
burden  in  the  furnace. 

*  Irwin,  Eng.  Mag.,  Oct.  IQOI,  abstr.  J.  Am.  Chem.  Soc.,  24,  40. 
f  H.  O.  Hofman,  Tech.  Quar.,  u,  212  (1898). 
%  Pennock,  J.  Am.  Chem.  Soc.,  21,  678  (1899). 


FUELS— SOLID,  LIQUID,  AND    GASEOUS.  65 

The  analysis  of  Connellsville  coke  with  the  coal 
from  which  it  is  prepared  is  given  below. 

Water.        Volatile  Matter.      Carbon.          Sulphur.  Ash. 

Coal          1.26  30.1  59.62  0.78  8.23 

Coke        0.03  1.29  89.15  0.084  9.52 

Otto-Hoffman  coke: 

Fixed  Carbon. 

3.7                  1.3                           86.1  8.9 

Heating   value 7100  C. 

The  Minor  Solid  Fuels. 

Sawdust  and  Spent  Tan-bark  find  occasional  use, 
their  value  depending  upon  the  quantity  of  moisture 
they  contain.  With  57  per  cent  of  moisture  I  pound 
of  tan-bark  gave  an  evaporation  of  4  pounds  of  water. 

"Wheat  Straw  finds  application  as  fuel  in  agricul- 
tural districts,  3!  pounds  being  equal  to  I  pound  of 
coal.  Upon  sugar-plantations  the  crushed  cane  or 
Bagasse,  partially  dried,  is  extensively  used  as  a 
fuel.  With  16  per  cent  of  moisture  an  evaporation 
of  2  pounds  of  water  per  pound  of  fuel  has  been 
obtained. 

Briquets/' Patent  Fuel/'* — In  Europe  coal  dust  is 
cemented  together  with  some  tarry  binding  material 
and  baked  or  compressed  into  blocks  usually  about 
6X2X1  inches,  which  form  a  favorite  fuel  for  domestic 
purposes.  In  some  cases  they  take  the  form  and  size 
of  a  large  goose  egg,  and  are  called  eggettes:  these  are 
being  made,  among  other  places,  at  Scranton,  Pa.,  and 
withstand  well  the  shocks  incident  to  shipment. 

*  Condition  of  the  Coal  Briquetting  Industry  in  the  United  States, 
E.  W.  Parker,  Bull.  No.  316  U.  S.  Geol.  Survey,  Contributions  to 
Economic  Geology,  1906.  Part  II,  Coal  Lignite  and  Peat,  pp. 
460-485. 


66  GAS    AND   FUEL  ANALYSIS. 

Storage  of  Coal  aud  Spontaneous  Combustion. — 

While  authorities  differ  as  to  the  way  and  manner  in 
which  coal  should  be  stored,  as  regards  height  of  pile, 
number,  size,  and  arrangement  of  ventilating  channels, 
they  are  practically  agreed  that  it  should  always  be 
covered.  Six  months'  exposure  to  the  weather  may  with 
European  coals  cause  a  loss  of  from  10  to  40  per  cent  in 
heating  value,  while  with  Illinois  coals  it  varies  from 
2  to  10  per  cent.*  The  North  German  Lloyd  Steamship 
Company  stores  its  coal  in  a  covered  bin  provided  with 
ventilators,  and  restricts  the  height  of  the  pile  to  8  feet. 
A  large  gas  company  in  a  western  city  also  uses  a  covered 
bin,  with  ventilators  8  inches  square  every  20  feet;  the 
height  of  the  pile  may  be  from  10  to  15  feet.  An  electric 
company  in  the  same  city  f  has  arranged  to  store  14,000 
tons  of  coal  under  water  in  12  pits,  a  steam-shovel  being 
used  to  dig  out  the  coal.  Ventilating  flues  serve  the 
additional  purposes  of  enabling  the  temperature  of  the 
pile  to  be  ascertained  before  ignition  takes  place,  and  as 
a  means  of  introduction  of  either  steam  or  carbonic  acid 
to  extinguish  any  fire  which  may  occur.  All  the  supports 
of  the  bin  in  contact  with  the  coal  should  be  of  brick, 
concrete  or  iron,  and  if  of  hollow  iron,  filled  with  cement. 
The  spontaneous  combustion  of  coal  is  due  primarily 
to  tne  rapid  absorption  of  oxygen  by  the  finely  divided 
coal,  and  to  the  oxidation  of  iron  pyrites,  "coal  brasses," 
occurring  in  the  coal. '  The  conditions  favorable  to 
the  process  are: 

*  Parr    and   Hamilton,    Univ.   of  111.,    Bulletin  4,  No.  33,  August, 
1907. 
f  Eng.  and  Min.  Jour.,  September  15,  1906. 


FUELS— SOLID,    LIQUID,    AND   GASEOUS.  67 

First.  A  supply  af  air  sufficient  to  furnish  oxygen,  but 
of  insufficient  volume  to  carry  off  the  heat  generated. 

Second.  Finely  divided  coal,  presenting  a  large  surface 
for  the  absorption  of  oxygen. 

Third.  A  considerable  percentage  of  volatile  matter  in 
the  coal. 

Fourth.     A  high  external  temperature. 

A  method  of  extinguishing  a  fire  in  a  coal  pile  not 
provided  with  ventilators  consists  in  removing  and  spread- 
ing out  the  coal  and  flooding  the  burning  part  with  water. 
Another  method  consists  in  driving  a  number  of  iron  or 
steel  pipes  provided  with  " driven  well  points"  at  the 
place  where  combustion  is  taking  place,  and  forcing 
water  or  steam  through  these  upon  the  fire. 

b.  LIQUID  FUELS. 

These  consist  of  petroleum  and  its  products,  and 
various  tarry  residues  from  processes  of  distillation, 
as  from  petroleum,  coking-ovens,  wood  and  shale. 
Liquid  fuel  possesses  the  advantage  that  it  contains  no 
ash,  is  easily  manipulated,  the  fire  is  of  very  equable 
temperature,  very  hot,  and  practically  free  from  smoke. 

Regarding  the  origin  of  petroleum,  many  theories 
have  been  proposed.  That  of  Engler,*  that  it  was 
formed  by  the  distillation  under  pressure  of  animal  fats 
and  oils,  the  nitrogenous  portions  of  the  animals  pre- 
viously escaping  as  amines,  seems  most  probable;  it 
has  yielded  the  best  results  of  any  hypothesis  when 
tested  upon  an  industrial  scale. 

*  Jour.  Soc.  Chem.  Industry,  14,  648. 


68  GAS  AND   FUEL   ANALYSIS. 

Crude  Petroleum  varies  greatly  in  color  according 
to  the  locality;  it  is  usually  yellowish,  greenish,  or 
reddish  brown,  of  benzine-like  odor,  and  sp.  gr.  of  0.78 
to  0.80.  It  "  flashes"  at  the  ordinary  temperature: 
hence  great  care  should  be  employed  in  its  use  and 
storage.  Its  percentage  composition  is  shown  below. 

Carbon.  Hydrogen. 

84.0-85.0  16.0-15.0 

It  is  more  than  twice  as  efficient  as  the  best  anthra- 
cite coal.  In  practice  14  to  16  pounds  of  water  per 
pound  of  petroleum  have  been  evaporated,  and  an 
efficiency  of  19,000  B.  T.  U.  was  obtained  as  against 
8500  B.  T.  U.  for  anthracite.  In  general  3^  to  4  bar- 
rels of  oil  are  equivalent  to  a  ton  of  good  soft  coal.* 

c.  GASEOUS  FUELS. 

% 

Natural  Gas  is  usually  obtained  when  boring  for 
petroleum  and  consists  mainly  of  methane  and  hydro- 
gen, although  the  percentage  varies  with  the  locality. 
The  Findlay,  Ohio,f  gas  is  of  the  following  composi- 
tion: 

CH4  H  N  O          C2H4        C02         CO  H,S        Sp  Gr. 

92.6          2.3          3.5  0.3          0.3          0.3          0.5          0.2          0.57 

Blast-furnace,  Producer,  or  Generator  Gas  is  the 
waste  gas  issuing  from  the  top  of  a  blast-furnace  or  ob- 
tained by  partially  burning  coal  by  a  current  of  air  (pro- 


*  W.  B.  Phillips,  Texas  Petroleum  (1900),  p.  84. 
f  Orton,  Geology  of  Ohio,  vol  vi.  p.  137. 


FUELS— SOLID,   LIQUID,  AND    GASEOUS.          69 

duced  by  steam)  in  a  special  furnace — a  gas-producer  or 
generator.     It  is  mainly  carbonic  oxide  and  nitrogen. 

co        N       co2      H     CH4   o    B-™-tper 

Blast-furnace  gas 343  63.7  0.6  1.4 

Gas  from  bitumin.  coal  24.5  46.8  3.7  17.8  6.8   0.4         223 

"       "         "            "  25.0  41.4  4.0  19.4  9.6   0.6 

"        "     anthrac.     "  27.0  57.3  2.5  12.0  1.2     — 

"          "          "  17.2  53.1  8.6  18.2  2.4  0.4          140 

"       "          "          "  26.0  47.0  8.0  18.5  0.5     —          145* 

One  ton  of  coal  yields  from  i6ot  to  170  thousand 
cubic  feet  of  gas  of  1 56  to  i  38  B.T.U.  heating  power,  or 
8 1  to  86  or  even  90  per  cent  of  the  value  of  the  coal. 

Water-gas. — If,  instead  of  passing  simply  air  over 
hot  coal,  water-vapor,  or  rather  steam,  be  employed, 
it  is  decomposed,  giving  carbonic  oxide  and  hydrogen, 
according  to  the  equation  H2O  -f-  C  =  CO  -f-  Ha ,  and 
the  resulting  mixture  is  called  water-gas.  The  per- 
centage composition,  which  varies  according  to  the  ap- 
paratus and  fuel  employed,  is  about  as  follows: 

CO  H         CH4      CO2         N  O        lilts.     Sp.  Gr. 

From  coke 45.8       45.7       2.0       4.0       2.0       0.5  0.57 

From  bit.  coal    34.0       41.9       7.5       5.4       9.2       i.i       0.9 

Fischer  {  states  that  I  ton  of  coke  gives  about  36 
thousand  cubic  feet  of  gas,  equivalent  to  42  per  cent 
of  the  value  of  the  coal.  From  I  ton  of  bituminous 
coal  about  51  thousand  cubic  feet  of  gas  of  360  B.T.U. 
heating  power  are  obtained,  or  an  efficiency  of  nearly 
62  per  cent.§ 


*  Suction  gas  producer. 

f  Humphrey,  Jour.   Soc.  Chem.  Industry,   20,    107  (1901);  ibid.,  16, 
522(1897). 
J  Taschenbuch  fur  Feuerungs-Technlker,  p.  27. 

§  Slocum,  J.  Soc.  Chem.  Industry,  16,  420  (1897). 


7° 


GAS  AND   FUEL   ANALYSIS. 


Coal  or  Illuminating  Gas  was  formerly  produced 
by  the  distillation  of  bituminous  coal;  it  is  at  present 
largely  made  by  the  enriching  of  water-gas.  ''Gas- 
oil,"  a  crude  naphtha,  is  blown  into  the  water-gas 
generator  and  changed  to  a  permanent  gas  by  the 
heat.  It  is  of  the  following  composition  : 

H        CH4        CO       C2H4     CO%    N        O     Sp.  Gr. 

Coal  gas 47.0     40.5       6.0       4.0     05     1.5     0.5      0.4 

Enriched  water-gas     27.9     25.9     25.3     15.0     2.9     3.0     o.o      0.6 

One  ton  of  coal  gives  about  io»thousand  cubic  feet  of 
gas,  or  about  20  per  cent  of  the  heating  value  of  the 
coal. 

Heating  Value  of  these  Gases. 

The  following  table,  mainly  from  Slocum,*  gives  an 
idea  of  the  comparative  value  of  the  gases : 


Name  of  Gas. 
Oil    

B.  T.  U.  per 
Cu.  Ft.t 

I  ^^O 

Yield. 
77  CU    ft 

Air  Required  /or 
Combustion 
per  Cu.  Ft. 

080      ' 

per  gal. 

0.80 

840-1170 
7OO 

Thousand  Ft. 
per  Ton. 

4O  t 

686 

5" 

Coal      

600-625 

IO 

«;.6«; 

332—  tjoo 

c 

Heating  (coke-oven). 

367 

a/12 

5 

Mond  producer  

ie;6 

1  60 

•V7 

I    2*> 

Siemens  producer.... 
Wood  or  peat  

137 
140-145 

170 

*  Slocum,  J.  Soc.  Chem.  Industry.  16,  420  (1897). 

f  Determined  with  ths  Junkers  calorimeter. 

\  168-200  gallons  of  "  gas-oil "  are  also  required. 


FUELS— SOLID,    LIQUID,    AND    GASEOUS.  71 

REFERENCES. — Report  of  U.  S.  "Liquid  Fuel"  Board, 
Dept.  of  Navy,  Bureau  of  Steam  Engineering,  Washington, 
1904.  pp.  450. 

Report  on  the  Operations  of  the  Coal-Testing  Plant  of 
the  U.  S.  Geological  Survey  at  St.  Louis,  1904.  Pro- 
fessional Paper,  No.  48,  Parts  I,  II,  and  II.  1906. 

Preliminary  Report  on  the  Operations  of  the  Coal  Testing 
Plant  of  the  U.  S.  Geol.  Survey  at  St.  Louis ,  1904. 

Bull.  No.  261,  1905. 

Bull.  No.  261  for  1905. 

Bull.  No.  290,  1906. 

A  Study  of  Four  Hundred  Steaming  Tests,  made  at 
Fuel  Testing  Plant  at  St.  Louis  in  1904,  1905,  1906,  by 
L.  P.  Breckenridge.  Bull.  No.  325,  U.  S.  Geol.  Survey, 
1907. 

The  Burning  of  Coal  without  Smoke.     D.  T.  Randall. 
Bull.  No.  334,  U.  S.  Geol.  Survey,  1908. 
Barr,  "Boilers  and  Furnaces" 
Hodgetts,  "  Liquid  Fuels." 


CHAPTER    VIII. 

METHODS    OF    ANALYSIS     AND     DETERMINATION 
ON   THE    HEATING   VALUE   OF    FUEL. 

SAMPLING. 

A  FEW  representative  lumps  or  shovelfuls  are  taken 
from  each  barrow  or  from  various  points  in  the  pile 
in  boiler  tests.  Shovelfuls  of  coal  should  be  taken  at 
regular  intervals  and  put  into  a  tight  covered  barrel 
or  some  air-tight  receptacle,  and  the  latter  should  be 
placed  where  it  is  protected  from  the  heat  of  the  fur- 
nace.* In  sampling  two  conditions  must  be  observed: 
First,  the  original  sample  should  be  of  considerable  size 
and  thoroughly  representative ;  and,  second,  the  quartering 
down  to  an  amount  which  can  be  put  into  a  sealed  "  light- 
ning" jar  should  be  carried  out  as  quickly  as  possible 
after  the  sample  is  taken.  Careful  samplings  and  careful 
treatment  of  samples  are  necessary  to  obtain  reliable 
results,  especially  in  the  determination  of  moisture. 
The  lumps  are  coarsely  broken,  and  the  whole  spread 
out  in  a  low  circular  heap.  Diameters  are  drawn 
at  right  angles  in  it  and  opposite  quarters  taken, 
and  treated  similarly  to  the  whole  sample.  The 
operation  is  continued  until  a  sample  of  a  few  pounds 
is  obtained.  This  is  roughly  crushed  and  samples 
taken  at  different  points  for  the  moisture  determi- 
nation ;  it  is  then  further  quartered  down  until  a 

*  Report  of  Committee  on  Coal  Analysis,  J.  Am.  Chem.  Soc., 
21,  1116  et  seq.  (1899). 

72 


FUEL    ANALYSIS— HEATING    VALUE.  73 

sample  of  100  grams  which  passes  a  6o-mesh  sieve  is 
obtained. 

The  methods  employed  in  the  analysis  of  fuels  are 
largely  a  matter  of  convention,  various  methods  giving 
varied  results;  for  example,  it  is  well-nigh  impossible 
to  obtain  accurately  the  percentage  of  moisture  in 
coal,  as  when  heated  sufficiently  hot  to  expel  the 
water  some  of  the  hydrocarbons  are  volatilized. 

Moisture- — Dry  one  gram  of  coal  in  an  open  cru- 
cible at  104°— 107°  C.  for  one  hour.  Cool  in  a  desic- 
cator and  weigh  covered.  Where  accuracy  is  required, 
determinations  must  also  be  made  on  the  coarsely 
ground  sample ;  this  latter  result  is  to  be  regarded  as 
the  true  amount  and  corrections  applied  to  all  deter- 
minations where  the  powdered  sample  is  used.*  f 

Volatile  Combustible  Matter  and  Coke.*§— Place 
one  gram  of  fresh,  undried  powdered  coal  in  a  platinum 
crucible  having  a  tightly  fitting  cover.  Heat  over  the 
full  flame  of  a  Bunsen  burner  for  seven  minutes  by 
the  watch.  The  crucible  should  be  supported  on  a 
platinum  triangle  with  the  bottom  six  to  eight  centi- 
meters above  the  top  of  the  burner.  The  flame 
should  be  fully  twenty  centimeters  high  when  burning 
free,  and  the  determination  should  be  made  in  a  place 
free  from  drafts.  The  upper  surface  of  the  cover 
should  burn  clear,  but  the  under  surface  should  remain 
covered  with  carbon.  To  find  "  Volatile  Combusti- 
ble Matter"  subtract  the  per  cent  of  moisture  from 
the  loss  found  here.  The  residue  in  the  crucible 
minus  the  ash  represents  the  Coke  or  Fixed  Carbon. 

*  Report  of  Committee  on  Coal  Analysis,  loc.  tit. 

f  See  also  an  article  by  Hale,  Proc.  Am.  Soc.  Mech.  Eng.  1896. 

§  Somrnermeier,  J.  A.  C.  S,  28,  1002  (1906). 


74 


GAS   AND    FUEL  ANALYSIS. 


Certain  non-coking  coals  suffer  mechanical  loss 
from  the  rapid  heating. 

Carbon  and  Hydrogen. — These  are  determined  by 
burning  the  coal  in  a  stream  of  air  and  finally  in 
oxygen,  the  products  of  combustion,  carbon  dioxide 
and  water,  being  absorbed  in  potassium  hydrate  and 
calcium  chloride. 

Apparatus  Required. — Combustion-furnace  similar 
to  that  shown  in  Fig.  15.  Combustion-tube  filled. 


FIG.  15.— COMBUSTION-FURNACE. 

Potash-bulbs  with  straight  chloride  of  calcium  tube 
filled.  Chloride  of  calcium  tube  filled.  Oxygen- 
holder,  drying  and  purifying  apparatus.  Porcelain 
boat,  desiccator,  tongs,  -J-inch  rubber  tubing.  Ana- 
lytical balance. 

The  combustion-tube  is  of  hard  glass,  i  inch  in  in- 
ternal diameter  and  36  inches  long,  closed  with  per- 
forated rubber  stoppers.  One  end — called  the  front 
end — is  filled  with  a  layer  of  copper  oxide  12  inches 
long,  held  in  place  by  plugs  of  asbestos  coming 


FUEL   ANALYSIS— HEATING    VALUE.  75 

within  4  inches  of  the  stopper.  In  coals  rich  in  sul- 
phur the  oxide  is  partially  replaced  by  a  layer  of 
chromate  of  lead  2  inches  long.  The  position  of  the 
boat  containing  the  coal  is  immediately  behind  this 
copper  oxide;  behind  the  boat  is  placed  an  oxidized 
copper  gauze  roll,  6  inches  long.  Before  making  the 
combustion,  the  tube  and  contents  should  be  heated 
to  a  dull  red  heat  in  a  stream  of  oxygen  freed  from 
moisture  and  carbon  dioxide  by  the  purifying  appa- 
ratus, to  burn  any  dust  and  dry  the  contents;  it  is 
then  ready  for  use. 

The  potash-bulbs  are  an  aggregation  of  five  bulbs, 
the  three  lowest  filled  with  potassium  hydrate  of  1.27 
sp.  gr.,  the  other  two  serving  as  safety-bulbs,  pre- 
venting the  liquid  from  being  carried  over  into  the 
connectors.  They  should  be  connected  further  with  a 
chloride  of  calcium  tube  to  absorb  any  moisture  carried 
away  by  the  dry  gas.  When  not  in  use  they  should 
be  closed  with  connectors  carrying  glass  plugs.  Before 
weighing  they  should  stand  at  least  fifteen  minutes  in 
the  balance-room  to  attain  its  temperature ;  the  weight 
should  be  to  milligrams  and  without  the  connectors. 

The  chloride  of  calcium  tube  is  of  U  form,  provided 
with  bulbs  for  the  condensation  of  the  water;  the 
granular  calcium  chloride  is  kept  in  place  by  cotton 
plugs,  and  the  stopper  neatly  sealed  in  with  sealing- 
wax.  As  calcium  chloride  may  contain  oxide  which 
would  absorb  the  carbon  dioxide  formed,  a  current  of 
dry  carbon  dioxide  should  be  passed  through  the  tube 
and  thoroughly  swept  out  by  dry  air  before  use. 

The  chloride  of  calcium  tube  like  the  potash-bulbs 
should  be  placed  in  the  balance-room  fifteen  minutes 


76  GAS    AND    FUEL    ANALYSIS. 

before  weighing  and,  if  the  balance-case  be  dry,  may 
be  weighed  without  the  connectors.  It  should  be 
weighed  to  milligrams. 

The  oxygen-holder  may  be  like  the  Muencke  aspi- 
rator, Fig.  14.  The  oxygen  should  be  purified  by 
passing  through  potassium  hydrate  and  over  calcium 
chloride. 

Operation. — The  front  stopper  of  the  combustion- 
tube  is  slipped  carefully  upon  the  stem  of  the  chloride 
of  calcium  tube  and  this  connected  to  the  potash- 
bulbs;  O.2  to  0.3  gram  of  the  coal  is  carefully 
weighed  into  the  porcelain  boat  (to  o.  I  mg.),  the  roll 
removed,  and  the  boat  inserted  behind  the  layer  of 
copper  oxide,  and  the  roll  and  stopper  replaced. 
The  tube  is  now  ready  to  be  heated. 

The  front  of  the  copper  oxide  is  first  heated,  the 
heat  being  gradually  extended  back;  at  this  time  the 
rear  end  of  the  copper  roll  is  heated  and  a  slow  cur- 
rent of  purified  air  passed  through.  This  method 
of  gradual  heating  of  the  tube  is  followed  until  the 
layer  of  copper  oxide  and  the  rear  portion  of  the  roll 
are  at  a  dull  red  heat.  Heat  is  now  cautiously  applied 
to  the  coal  and  the  current  of  air  slackened.  The 
volatile  matter  in  the  coal  distils  off,  is  carried  into 
the  layer  of  copper  oxide  and  burned;  the  carbon 
dioxide  formed  can  be  seen  to  be  absorbed  by  the 
potassium  hydrate.  When  this  absorption  almost 
ceases,  oxygen  is  turned  on  and  the  coal  heated  until 
it  glows.  The  stream  of  oxygen  should  be  so  regulated 
as  to  produce  but  two  bubbles  of  carbon  dioxide  in 
the  bulbs  per  second.  If  the  evolution  be  faster,  the 
gas  is  not  absorbed.  When  the  coal  has  ceased  glow- 


FUEL   ANALYSIS— HEATING    VALUE.  77 

ing,  oxygen  is  allowed  to  pass  through  the  apparatus 
until  a  spark  held  at  the  exit  of  the  last  chloride  of 
calcium  tube  (on  the  bulbs)  re-inflames;  the  oxygen  is 
allowed  to  run  for  fifteen  minutes  longer.  The  current 
of  oxygen  is  now  replaced  by  purified  air,  and  the 
heat  moderated  by  turning  down  the  burners  and 
opening  the  fire-clay  tiles;  the  air  is  allowed  to  run 
through  for  twenty  minutes  to  thoroughly  sweep  out 
all  traces  of  carbon  dioxide  and  moisture.  The  bulbs 
and  U  tube  are  disconnected,  stopped  up,  allowed  to 
stand  in  the  balance-room,  and  weighed  as  before. 
The  increase  in  weight  in  the  bulbs  represents  the 
carbon  dioxide  formed;  this  multiplied  by  the  factor 
0.2727  gives  the  carbon.  Similarly  the  increase  in  the 
U  tube,  minus  the  water  due  to  the  moisture  in  the 
coal,  represents  the  water  formed,  one  ninth  of  which 
is  hydrogen. 

Notes, — At  no  time  in  the  combustion  should  any 
water  appear  near  the  copper  roll,  as  it  is  an  indication 
that  the  products  of  combustion  have  gone  backward 
into  the  purifying  apparatus  and  hence  are  lost.  Such 
analyses  should  be  repeated.  Should  moisture  appear 
in  the  front  end,  it  may  be  gently  heated  to  expel  it. 
Both  ends  of  the  tube  should  be  frequently  touched 
with  the  hand  during  the  combustion,  and  should  be 
no  hotter  than  may  be  comfortably  borne,  as  the 
stoppers  give  off  absorbable  gases  when  highly  heated. 
Care  should  be  taken  not  to  heat  the  tube  too  hot, 
fusing  the  copper  oxide  into  and  spoiling  it.  One 
tube  should  serve  for  a  dozen  determinations.  It 
should  not  be  placed  upon  the  iron  trough  of  the 


jS  GAS    AND    FUEL    ANALYSIS. 

furnace,   but   upon   asbestos-paper  in   the   trough,  to 
prevent  fusion  to  the  latter. 

As  will  be  seen,  the  execution  of  a  combustion  is 
not  easy,  and  should  only  be  intrusted  to  an  experi- 
enced chemist.  The  results  obtained  are  usually  o.  I 
per  cent  too  low  for  carbon  and  a  similar  amount  too 
high  for  hydrogen. 

Ash. — This  is  determined  by  weighing  the  residue 
left  in  the  boat  after  combustion,  or  by  completely 
burning  one  gram  of  the  coal  contained  in  a  platinum 
dish;  often  a  stream  of  oxygen  is  used. 

Nitrogen  is  determined  by  Kjeldahl's  method, 
which  consists  in  digesting  the  coal  with  strong  sul- 
phuric acid,  aided  by  potassium  permanganate,  until 
nearly  colorless.  The  nitrogenous  bodies  are  changed 
to  ammonia,  which  forms  ammonium  sulphate  and 
may  be  determined  by  rendering  alkaline  and  distil- 
ling the  solution. 

Sulphur  is  determined  by  Eschka's  method,  con- 
sisting in  heating  for  an  hour  one  gram  of  the  coal 
mixed  with  one  gram  of  magnesium  oxide  and  0.5 
grm.  sodium  carbonate  in  a  platinum  dish  without  stir- 
ring, using  an  alcohol-lamp,  as  gas  contains  sulphur. 
It  is  allowed  to  cool  and  rubbed  up  with  one  gram  of 
ammonium  nitrate  and  heated  for  5  to  10  minutes 
longer.  The  resulting  mass  is  dissolved  in  200  cc.  of 
water  evaporated  to  150  cc.,  acidified  with  hydro- 
chloric acid,  filtered,  and  sulphuric  acid  deter- 
mined in  the  filtrate  in  the  usual  way  with  barium 
chloride. 

Oxygen  is  determined  by  difference,  there  being 
no  direct  method  known. 


FUEL   ANALYSIS — HEATING    VALUE.  79 

ANALYSIS    OF    LIQUID   FUELS. 

Carbon  and  Hydrogen. — This  determination  is 
made  as  in  the  case  of  the  solid  fuels,  the  liquid  being 
contained  in  a  small  bulb  sealed  for  weighing  to  prevent 
volatilization.  The  stem  is  scratched  and  broken  off 
and  the  bulb  inserted  in  the  combustion  tube  in  place  of 
the  boat.  Extra  care  in  heating  has  to  be  observed  to 
prevent  the  liquid  from  passing  through  unburnt.  For 
thick  or  tarry  oils  having  a  small  quantity  of  volatile 
matter,  the  boat  may  be  used  as  with  solid  fuels. 

Sulphur. — For  oils  containing  more  than  o.oi  per  cent 
sulphur  the  well  known  method  of  Carius  may  be  em- 
ployed. This  consists  in  sealing  up  the  oil  contained  in 
a  small  weighing  tube,  in  a  tube  with  fuming  nitric  acid 
and  barium  chloride  and  heating  in  a  furnace  for  several 
hours.  All  sulphur  is  converted  into  sulphuric  acid, 
which  combines  with  the  barium  chloride  forming  barium 
sulphate,  which  is  filtered  off  and  weighed  in  the  usual 
way.  Another  method  consists  in  burning  the  oil  in  a 
small  lamp  and  collecting  the  products  of  combustion. 
The  lamp  is  a  miniature  "oil  lamp"  made  from  a  3-inch 
test-tube  (weighing  tube)  by  drawing  a  piece  of  weighed 
lamp  wicking  through  a  small  glass  tube  contained  in  the 
stopper.  This  lamp  is  suspended  by  a  wire  from  the 
balance  and  weighed  accurately. 

It  is  lighted  and  hung  under  a  funnel  arranged  so  that 
the  products  of  combustion  are  drawn  by  an  air-pump 
through  a  series  of  two  washing  bottles  containing  satu- 
rated bromine  water.  After  about  a  gram  of  oil  has  been 
burned  (about  1.3  cc.)  the  wick  is  carefully  removed 
without  losing  any  oil,  the  stopper  replaced  and  the  tube 


80  GAS  AND  FUEL  ANALYSIS. 

again  weighed.  The  wick  and  oil  it  contains  are  covered 
with  Eschka's  mixture  and  treated  as  for  the  determina- 
tion of  sulphur  in  coal  (p.  78).  The  hydrochloric  ac:d 
nitrate  is  added  to  the  bromine  solution,  the  bromine 
boiled  out,  the  solution  evaporated  to  about  150  cc.,  and 
the  sulphuric  acid  formed  determined  in  the  usual  way 
with  barium  chloride. 

The  oil  burned  is  obviously  the  weight  of  the  lamp 
before  and  after  burning  less  the  weight  of  the  dry  wick. 
This  treatment  of  the  wick  is  necessary,  as  Conradson  * 
has  found  sometimes  40  per  cent  of  the  sulphur  in  the  wick. 

Barlow 'sf  method  is  excellent,  but  requires  consider- 
able experience  to  carry  out. 

Nitrogen  is  determined  exactly  as  in  the  case  of  solid 
fuels. 

Water  can  be  shown  qualitatively  by  the  cosine  test,J 
by  rubbing  with  a  little  eosine  on  a  glass  plate.  If  water 
be  present  the  oil  will  take  on  a  pink  color.  For  its 
quantitative  determination  a  weighed  amount  of  gently 
ignited  plaster  of  Paris  is  added  to  the  oil  and  allowed 
to  stand  24-36  hours.  Gasoline  is  now  added  to  the  oil 
and  the  whole  brought  upon  a  dried  weighed  filter  and  the 
plaster  washed  until  all  oil  is  removed ;  the  filter  and  con- 
tents are  dried  at  a  gentle  heat  not  exceeding  100°  C.  to 
a  constant  weight.  The  increase  in  weight  represents 
the  quantity  of  water  in  the  oil. 

Flash  and  Fire  Test. — Determined  by  heating  the 
oil  in  the  covered  New  York  tester  or  lubricating  oil  tester 
according  to  Gill,  "  Short  Handbook  of  Oil  Analysis," 
Chapters  I  and  II. 

The  analysis  of  gaseous  fuels  has  already  been  de- 
scribed in  Chapter  V.  

*  J.  Ind.  and  Eng.  Chem.,  2,  171  (1910). 

f  J.  Am.  Chem.  Soc.,  26,  341  (1904). 

I  Holley  and  Ladd,  Mixed  Paints,  Color  Pigments  and  Varnishes,  p.  36. 


FUEL  ANALYSIS— HEATING    VALUE.  8 1 

DETERMINATION    OF   CALORIFIC    POWER   OF   SOLID 
AND    LIQUID    FUEL. 

a.   Direct  Methods. 

Many  forms  of  apparatus  have  been  proposed 
for  this  purpose ;  few,  however,  with  the  exception 
of  those  employing  Berthelot's  principle — of  burning 
the  substance  under  a  high  pressure  of  oxygen — 
have  yielded  satisfactory  results.  The  apparatus  of 
William  Thomson,*  and  also  that  of  Barrus,  in  which 
the  coal  is  burnt  in  a  bell-jar  of  oxygen,  while  usually 
yielding  results  within  3  per  cent  of  the  calculated 
value,  yet  they  may  vary  as  much  as  8  per  cent 
from  that  value. f  Unless  a  crucible  lined  with 
magnesia  be  used,  or  the  sample  mixed  with  bitumin- 
ous coal,  it  is  inapplicable  to  certain  semi-bitumin- 
ous and  anthracite  coals,  as  the  ash  formed  over 
the  surface  prevents  the  combustion  of  the  coal 
beneath  it. 

Fischer's  calorimeter^:  is  similar  in  principle,  but  is 
claimed  to  give  very  good  results. § 

Lewis  Thompson's  calorimeter,  in  which  the  coal  is 
burnt  in  a  bell-jar  by  the  aid  of  oxygen  furnished  by 
the  decomposition  of  potassium  chlorate  or  nitrate,  is 
open  to  several  objections,  the  chief  of  which  are: 
I.  The  evolution  of  heat  due  to  the  decomposition  of  the 


*  Thomson,  Jour.  Soc.  Chemical  Industry,  5,  581. 
f  Ibid.,  8,  525. 

\  Zeit.  f.  angewandte  Chemie,  12,  351. 

§  Bunte,  Jour.  f.  Gasbeleuchtung  und  Wasserversorgung,  34, 
21,  41. 


82  GAS   AND    FUEL    ANALYSIS. 

oxidizing  substance  used.  2.  Loss  of  heat  due  to 
moisture  carried  off  by  the  gases  in  bubbling  through 
the  water.  The  results  which  it  gives  must  be  in- 
creased by  15  per  cent.* 

Hempel's  apparatus  J  makes  use  of  the  Berthelot 
principle:  the  coal  must  be  compressed  into  a  cylindei 
for  combustion — a  process  to  which  every  coal  is  not 
adapted  —  only  applicable  to  certain  varieties  of 
bituminous  and  brown  coal.  The  mixture  with  the 
coal  of  any  cementing  or  inflammable  substance  to 
form  these  cylinders  carries  with  it  the  necessity  of 
accurately  determining  its  calorific  power  beforehand. 

The  best  apparatus  for  the  purpose  is  probably  that 
of  Mahler  |§  modified  by  Williams,  Norton,  and  Emerson, 
the  modifications  consisting  in  replacing  the  enamel  lining 
by  a  nickel  one  or  by  electroplating  the  inside  with  gold 
and  in  improved  methods  of  making  the  apparatus 
tight. 

The  Mahler  apparatus,  Fig.  17,  consists  of  a  mild- 
steel  cylinder^,  with  walls  half  an  inch  thick,  narrowed 
at  the  top  for  connection  by  a  screw-joint  with  the 
cover  carrying  the  vessel  C  to  contain  the  coal.  This 
cylinder  or  bomb  is  placed  inside  the  calorimeter  D, 
and  this  inside  a  jacket  A.  At  the  right  is  shown  a 
portion  of  the  oxygen-cylinder  and  the  gauge. 

For  the  following  directions  for  its  use  the  author 
is  indebted  to  the  kindness  of  Professor  Silas  W. 
liolman  of  the  Institute  of  Technology. 

*  Scheurer-Kestner,  J.  Soc.  Chem.  Industry,  7,  869  (1888). 
t  Mahler,  id.  n,  840  (1892). 
j  Hempel,  Gasanalytische  Methoden,  p.  347. 
§  Mayer,  Stevens  Indicator  (1895),  X34- 

**  For  pressures  developed  in  bomb,  see  Benedict  and  Fletcher,  J.  Am. 
Chem.  Soc.,  29,  739  (1907). 


FUEL   ANALYSIS— HEATING    VALUE. 


8,5 


Preparation   of  Bomb. — Remove   the    ring   upon 

which  it  sits  in  the  calorimeter. 

Wash  out  the  bomb.  It  need  not  be  dry.  Leave 
cover  off. 

See  that  the  1  ead- ring  washer  P,  Fig.  16,  is  in  good 
condition.  Unless  its  upper  surface 
is  fairly  smooth  the  cover  cannot  be 
tightly  closed.  Repeated  screwing 
on  of  the  cover  raises  a  burr  of  lead. 
When  this  becomes  noticeable  it  must 
be  removed  by  cutting  with  a  knife- 
blade.  If  there  is  difficulty  in  mak- 
ing the  cover  tight,  it  is  most  likely 
to  be  due  to  this  cause. 

Grease  the  screw  5  upon  the  out- 
side of  the  bomb  slightly  with  tallow 
or  a  heavy  oil,  but  be  sure  that  none 
of  the  grease  gets  beyond  the  lead 
washer. 
FIG.  ^.-MAHLER'S  Secure  the  bomb  very  firmly  in  the 

BOMB.  heavy  clamp  on  the  table. 

Place  the  top  on  a  ring  or  in  a  clamp  of  a  lamp-stand 
and  in  an  upright  position. 

Put  in  position  the  platinum  tray  C  and  the  rod  E, 
Fig.  17. 

Twist  on  the  loop  of  ignition-wire  (fine  platinum 
or  iron).  This  must  make  good  electrical  contact 
with  both  E  and  the  pan  or  its  supporting  rod. 
Failing  this  the  current  will  not  flow  to  fuse  the  wire. 
Failure  to  ignite  is  almost  always  traceable  to  this 
cause. 

Pour  into  the  tray  a  known  weight  of  the  substance 


84  GAS   AND   FUEL   ANALYSIS. 

to  be  burned.  If  this  be  coal,  slightly  over  one  gram 
should  be  used.  It  is  usually  best  inserted  from  a 
small  test-tube  weighed  before  and  after,  with  due 
precautions  against  loss. 

The  ignition-wire  should  dip  well  into  the  coal. 

The  fineness  required  in  the  combustible  depends 


FIG.  17. — MAHLER'S  APPARATUS  COMPLETE. 

upon  its  nature.  Anthracite  coal  should  be  in  a  very 
fine  powder,  at  least  100  mesh.  Trial  will  show  whether 
any  unburned  grains  remain,  indicating  that  the  com- 
bustible is  too  coarse. 

The  standard  which  carries  the  pressure-gauge 
should  be  screwed  to  the  table  near  the  bomb-clamp, 
and  the  oxygen  cylinder  must  be  placed  near  by  so 
that  the  three  may  be  easily  connected  by  the  flexible 
copper  tube. 


FUEL   ANALYSIS— HEATING   VALUE.  85 

The  top  carrying  the  charge  is  then  cautiously  (to 
avoid  loss  of  charge  by  jarring  or  draft)  transferred  to 
the  bomb  and  screwed  carefully  home.  The  lifting  is 
best  done  by  hooking  the  fingers  beneath  the  milled 
head  at  the  top  of  the  valve-screw  R.  The  top  must 
be  set  up  hard  by  the  wrench  which  takes  the  large 
nut  cut  on  the  cover.  In  setting  this  up  it  is  desirable 
to  use  no  more  force  than  is  necessary  to  secure  a  gas- 
tight  bearing  of  the  tongue  of  the  cover  against  the 
lead  Avasher  P.  Just  the  force  required  can  only  be 
learned  by  experience,  but  it  is  always  considerable. 
A  slight  leak  is  unimportant,  but  it  is  not  difficult  to 
secure  a  tight  seal  if  the  lead  washer  be  kept  in  good 
condition. 

To  fill  with  oxygen  proceed  as  follows: 

Screw  down  the  valve-screw  R  gently  to  close  the 
valve.  Connect  the  copper  tube  to  the  oxygen-tank 
gauge,  and  to  the  bomb  at  N.  See  that  there  are 
leather  washers  at  the  joints.  Turn  the  connecting 
nuts  firmly  but  not  violently  home.  The  connections 
to  the  oxygen-tank  and  gauge  are  usually  left  undis- 
turbed, and  only  that  at  N  has  to  be  made  each  time. 

It  is  now  necessary  to  test  for  leakage  in  the  con- 
nections. To  do  this,  as  R  is  closed,  it  is  only  neces- 
sary to  open  the  oxygen-tank  cautiously  by  means  of 
its  wrench  until  the  gauge  indicates  5  or  10  atmos- 
pheres and  then  close  it.  As  the  tank  when  freshly 
charged  has  a  pressure  of  120  atmospheres,  and  the 
gauge  reads  only  to  35  atmospheres,  care  must  be  used 
in  all  manipulations  not  to  overstrain  the  gauge,  also 
avoid  suddenly  releasing  the  pressure  on  the  gauge. 
When  this  pressure  is  on,  any  leak  in  the  connections 


86  GAS   AND    FUEL    ANALYSIS. 

will  be  indicated  by  a  drop  in  the  gauge  reading.  If 
a  leak  exists,  it  must  be  removed  or  rendered  extremely 
slow  before  proceeding  further.  It  is  most  likely  to 
be  found  in  the  joints,  which  must  be  tightened  one 
by  one  until  the  leak  stops. 

Now  to  fill  the  bomb  it  is  next  necessary  to  open 
/?.  This  could  be  done  by  merely  turning  back  the 
milled  head,  or  the  nut  just  above  it.  But  as  this 
would  put  a  twist  into  the  copper  connecting-tube 
(which  many  times  repeated  would  break  it),  the  better 
way  is,  holding  one  wrench  in  each  hand,  to  loosen 
the  connecting  nut  above  N  by  a  half-turn,  holding  R 
by  the  wrench  and  nut,  then  to  turn  the  nut  open 
a  half-turn  or  until  it  is  again  tight  in.  This  leaves 
the  connections  tight  and  R  open  into  the  bomb.  The 
oxygen  is  then  turned  slowly  on,  and  the  bomb 
gradually  fills.  If  a  gram  of  coal  is  to  be  burned,  a 
pressure  of  25  atmospheres  gives  the  proper  amount  of 
gas  in  the  bomb.  Note  that  the  valve  R  and  the  inlet- 
tube  have  small  borings.  Thus  the  inflow  of  gas  will 
be  slow  and  the  pressure  in  the  connecting-tube  will 
be  higher  than  in  the  bomb.  If,  therefore,  the  tank 
be  closed  quickly,  the  gauge-reading  will  fall  somewhat 
until  these  pressures  equalize,  and  will  then  remain 
stationary  unless  there  is  a  leak.  The  tank-cock  must 
always  be  kept  well  under  control  to  avoid  overcharg- 
ing either  gauge  or  bomb. 

When  the  bomb  is  full,  close  first  the  tank-cock. 
Then,  to  close  R,  put  the  wrenches  on  the  nuts  and, 
holding  one  from  turning,  set  the  other  down  until  R 
is  tight,  but  not  too  tig/it.  Avoid  straining  7?,  which 
closes  tight  very  easily.  By  this  method  the  copper 


FUEL   ANALYSIS— HEATING    VALUE.  87 

tube  is  not  twisted.  There  is  of  course  a  slight  leak 
of  gas  from  the  bomb  after  N  leaves  the  nut  and 
before  R  is  closed,  but  the  time  required  for  the  half- 
turn  is  so  short  and  the  outflow  so  slow  that  the  loss 
is  insignificant.  There  is  no  need  to  hurry  in  this 
operation.  Be  deliberate  and  careful  of  the  apparatus. 
A  valve  like  R  is  a  nice  piece  of  workmanship,  and  to 
endure  much  usage  it  must  be  treated  with  care. 

The  bomb  is  now  ready  to  be  undamped  and  set 
into  the  ring  preparatory  to  transfer  to  the  calorimeter. 
It  can  be  left  standing  indefinitely,  but  must  be 
handled  with  caution  (best  by  lifting  with  fingers 
beneath  R,  to  avoid  spilling  the  charge). 

Preparation  of  Calorimeter. — The  outer  jacket  of 
the  calorimeter  should  be  filled  with  water  at  about 
the  room  temperature  or  a  few  degrees  higher.  If 
left  standing  from  day  to  day  it  will  usually  be  nearly- 
enough  right.  It  is  well  to  stir  it  (blow  air  through 
•it)  somewhat  before  beginning  work,  if  it  has  stood  for 
some  time. 

Be  sure  that  the  inner  surface  of  this  jacket,  i.e., 
the  one  which  is  next  the  calorimeter,  is  thoroughly 
dry,  and  do  not  let  any  water  spill  into  it — or  remove 
it  if  it  does  so. 

Thoroughly  dry  the  outer  surface  of  the  calorimeter 
and  keep  it  so.  Moisture  depositing  on  or  evaporating 
from  the  surface  of  the  calorimeter  is  sure  to  cause  an 
irregular  error  which  may  spoil  otherwise  good  work. 

Put  the  calorimeter  in  place.  Transfer  the  bomb  to 
it,  and  adjust  the  stirrer  so  that  it  works  properly. 

Pour  in  the  proper  amount  of  water,   about  2.25 


88  GAS  AND  FUEL  ANALYSIS. 

liters,  at  a  suitable  temperature,  best  by  using  marked 
flasks  carefully  calibrated  beforehand. 

Insert  the  thermometer. 

See  that  the  electrical  attachments  are  ready  for 
instantaneous  use.  The  whole  is  then  ready  for  the 
combustion. 

Combustion  Observations. — With  apparatus  all  in 
place  run  the  stirrer  briskly  and  continuously  until 
the  completion  of  the  work.  Allow  about  five  minutes 
for  everything  to  come  to  a  normal  condition.  Then 
take  temperature  readings  to  at  least  0.01°  at  each 
quarter  minute  for  at  least  five  minutes.  Record  the 
times  (h.  m.  s.)  and  corresponding  thermometer-read- 
ings, thus: 

Time.  Temp.  Remarks. 

2b  15'"   os  i5°-24  After  5m  stirring 


15 

.24 

30 

•  25 

45 

•  25 

16  o 

•  25 

15 

.26 

30 

.26 

15 

15.6 

30 

.9 

45 

16.2 

26  o 

.5 

etc. 

etc. 

Coal  ignited 


Exactly  at  the  beginning  of  a  noted  minute  close 
the  electric  circuit  through  the  fuse-wire.  If  the 
arrangements  are  right,  this  will  cause  the  coal  to 
ignite  at  once  and  the  combustion  is  almost  instan- 
taneous. Owing  to  the  time  required  to  transmit  the 


FUEL  ANALYSIS— HEATING   VALUE.  89 

heat  through  the  bomb  to  the  water,  the  temperature, 
however,  will  continue  to  rise  for  two  or  three  minutes. 
Keep  up  the  steady  stirring  and  the  quarter-minute 
temperature-readings  for  at  least  ten  minutes  after 
ignition,  recording  as  above.  One  or  two  observations 
may  be  unavoidably  lost  before  and  after  ignition,  but 
this  does  not  materially  affect  the  results.  The  read- 
ings during  the  rapid  rise  are  also  less  close. 

As  soon  as  the  rise  begins  to  slow  down,  however, 
the  hundredths  of  a  degree  must  again  be  secured. 
This  makes  a  series  of  observations  of  15  to  20 
minutes'  duration.  The  use  of  the  readings  to  obtain 
the  cooling  correction  and  the  corrected  rise  of  tem- 
perature of  the  calorimeter  is  given  under  the  heading 
"  Cooling  Correction  "  farther  on. 

This  completes  the  observations  unless  it  is  desired 
to  test  the  character  of  the  products  of  combustion. 
The  bomb  should  now  be  opened  and  rinsed,  as  the 
nitric  acid  formed  by  the  oxidation  of  the  nitrogen  in 
the  coal  and  air  attacks  the  metallic  lining  unless  it  be 
of  gold.  Also  the  top  is  more  easily  unscrewed  at 
first  than  later.  Leave  the  top  off. 

Before  unscrewing  the  top  of  the  bomb  be  sure  to 
open  the  valve  R  to  relieve  the  presure. 

Heat  Capacity  of  Bomb  and  Calorimeter. — The 
heat  capacity  of  the  bomb  may  be  found : 

1.  From  the  weights  and  assumed  specific  heats  of 
the  parts. 

2.  By  raising  the  bomb  to  an  observed  high  tem- 
perature and  immersing  in  water,  i.e.,   by  the  usual 
"  method  of  mixtures." 

3.  By  burning  in  it  a  substance  of  known  heat  of 


QO     '  GAS  AND  FUEL  ANALYSIS. 

combustion,  such  as  pure  naphthaline,  and  calculating 
back  to  find  the  heat  capacity  of  the  bomb. 

The  first  method  is  not  reliable.  Errors  of  several 
per  cent  may  enter  in  the  assumed  specific  heats. 

The  second  method  is  very  difficult  of  exact  per- 
formance, owing  to  the  size  and  form  of  the  bomb. 

The  third  method  is  by  far  the  most  reliable,  but  of 
course  depends  on  the  correctness  of  the  assumed  heat 
of  combustion  of  the  substance  used.  That  of  naphtha- 
line has  been  so  well  determined  by  Berthelot  and 
others,*  and  the  substance  is  so  easily  and  cheaply 
obtained  in  a  pure  state,  that  dependence  can  be 
placed  on  the  results.  This  method  has  the  great 
advantage  that  it  involves  the  use  of  the  apparatus  in 
precisely  the  same  way  as  in  subsequent  determina- 
tion, so  that  any  systematic  errors  of  method  tend  to 
cancel  one  another.  It  also  determines  at  the  same 
time  the  heat  capacity  of  the  calorimeter  and  stirrer 
just  as  used. 

The  capacity  of  the  calorimeter  and  stirrer  may 
best  be  determined  in  connection  with  that  of  the 
bomb  by  the  third  method  just  described.  Otherwise 
it  may  be  found  by  the  first  method,  or  by  a  method 
similar  to  the  second,  viz.,  by  pouring  into  the  calorim- 
eter when  partly  full  water  of  a  known  temperature 
different  from  that  of  the  water  in  the  calorimeter, 
noting  all  temperatures  and  weights.  This  last 
method,  however,  is  very  unsatisfactory  in  practice 
owing  to  the  small  heat  capacity  of  the  calorimeter 
and  to  the  losses  of  heat  in  pouring  the  water,  etc. 

*  i  gram  of  naphthaline  evolves  9692  C.     This  is  the  average  of 
150  determinations  by  four  different  obervers. 


FUEL   ANALYSIS—  HEATING    VALUE.  91 

A  general  expression  for  computing  the  heat  of 
combustion  from  the  bomb  observations  is  as  follows: 
Let  n  represent  the  number  of  grams  of  combustible, 
H  the  heat  of  combustion  sought,  W  the  weight  of 
water  in  the  calorimeter,  and  k  the  heat  capacity, 
or  water  equivalent,  of  bomb,  calorimeter,  stirrer, 
thermometer,  etc.  ;  tl  and  t^  represent  the  initial  and 
final  temperatures  of  the  water.  Then 

nH=  W(t,-  /,)  -f  t(f,  -/,), 
whence 


This  expression  is  exact  if  /a  is  corrected  for  loss  by 
cooling  as  described  in  the  methods  for  *'  Cooling 
Correction,"  p.  85. 

The  value  of  k  may  be  determined  by  either  of  the 
following  methods;  a  simplification  may,  however,  be 
introduced  which  will  save  much  labor  if  an  accuracy 
of  not  more  than  about  one  per  cent  is  sought,  pro- 
vided that  k  is  found  by  burning  naphthaline  or  other 
known  substance.  Use  enough  of  this  substance  to 
cause  about  the  same  rise,  /2  —  /,  ,  (within  i°)  as  will  be 
caused  by  one  gram  of  coal.  Omit  the  cooling  correc- 
tion entirely,  using  for  /2  the  maximum  temperature 
attained.  Then  compute  k\  this  value  will  be  erro- 
neous by  a  small  amount  owing  to  the  neglect  of  the 
correction.  Now  in  subsequent  measurements  on  coal 
also  neglect  the  cooling  correction,  using  for  /a  the 
maximum  observed  temperature  as  before,  thus  leav- 
ing an  error  in  /2.  Since  the  rise  /,  —  tl  in  both  cases 
will  be  nearly  the  same,  the  error  in  k  will  almost 


92  GAS  AND   FUEL   ANALYSIS. 

exactly  affect  that  in  A,  in  the  coal-test,  and  the  result- 
ing value  of  H  will  »be  nearly  free  from  this  error. 
This  method  of  course  implies  that  W  is  nearly  con- 
stant and  that  tl  is  systematically  arranged  to  be  either 
about  at  the  air-temperature  or  a  definite  amount 
below  it,  as  described  under  "  Cooling  Correction," 
so  that  the  cooling  loss  is  about  the  same.  The  time- 
interval  from  /j  to  /3  must  for  the  same  reason  be 
nearly  constant  in  all  cases. 

Cooling"  Correction. — In  all  careful  calorimetric 
work,  one  of  the  most  troublesome  sources  of  error  is 
the  loss  or  gain  of  heat  by  the  calorimeter  from  its 
surroundings.  This  loss  or  gain  is  due  to  radiation, 
to  air-convection  currents,  and  to  evaporation  or  con- 
densation. Unavoidable  irregularities  in  the  condi- 
tions and  the  smallness  of  the  quantities  to  be  measured 
render  the  amount  of  the  correction  variable  and  its 
determination  uncertain.  Many  methods  of  making 
the  correction  have  been  proposed.  One  of  the  best 
of  these  is  the  first  of  the  two  given  below,  but  the 
second,  although  a  little  more  troublesome  in  the 
execution  of  the  work,  appears  to  be  more  trustworthy 
in  its  results.  The  second  method  is  to  be  used. 

First  Method. — This  is  described  in  the  Physical 
Laboratory  Notes,  I*  under  "  Specific  Heat  of  Solids." 
In  this  method  the  water  at  the  outset  should  be  at 
such  a  temperature  that  it  is  gaining  very  slowly. 
For  an  open  calorimeter  this  is  about  i°  or  2°  below 
the  air-temperature,  but  varies  with  circumstances. 
Water  which  has  been  long  standing  in  the  room  is 
generally  about  right. 

Second  MetJiod. — For    the    discussion    and    detail; 


*  Obtainable  from  A.  D.  Machlachlan,  Bookseller,  Boston. 


FUEL  ANALYSIS— HEATING   VALUE. 


93 


reference  may  be  had  to  an  article  by  Professor  Holman 
in  Proc.  American  Academy  of  Arts  and  Sciences,  1 895 , 
p.  245  ;  also  in  The  Technology  Quarterly,  8,  344. 

Parr's  Calorimeter.* — This  "  has  the  advantage  of 
operating  without  an  oxygen  gas  supply ;  its  manipu- 
lation is  simple  and  the  extraction  of  the  heat  rapid, 
owing  to  the  compact  mass  in  which  the  heat  is  gen- 
erated. It  is  especially  adapted  to  soft  coal,  and 
while  designed  for  technical  purposes,  its  factor  of 
error  is  well  within  o.  5  per  cent."  "  It  depends  for  its 
action  upon  the  liberation  of  oxygen  from  a  compound 
which  shall  in  turn  absorb  the  products  of  combustion, 

conditions  admirably  met  in 
sodium  peroxide;  this  ob- 
viates the  necessity  of  pro- 
viding for  an  outlet  for  those 
gases  and  also  any  loss  aris- 
ing from  the  heat  they 
might  carry  off." 

"A,  Fig.  18,  is  the  calor- 
imeter of  about  two  liters 
capacity,  insulated  by  two 
outer  vessels  of  indurated 
fiber,  B  and  C,  so  placed  as 
to  provide  further  insulation 
by  the  air-spaces  b  and  c. 
FIG.  18.— PARR'S  CALORIMETER.  The  cover  is  double,  to  cor- 
respond, with-  an  air-space  between,  the  two  parts 
being  connected  for  convenience  in  handling.  The 
cartridge  D  has  a  capacity  of  about  25  cc.  ;  it  rests 
on  a  pivot  below,  extends  through  the  covers,  and  has 
a  small  removable  pulley  at  the  end.  Turbine  wings 


*  Parr,  J.  Am.  Chem.  Soc.,  22,  646  (1900). 


94  GAS  AND   FUEL   ANALYSIS. 

fastened  to  spring  clips  are  placed  on  the  cartridge, 
and  a  short  cylinder  E,  open  at  both  ends,  is  provided 
for  directing  the  current  set  up  by  rotation  of  the 
vanes  attached  to  the  cartridge.  The  stem  G  of  the 
cartridge  is  so  arranged  as  to  permit  the  passage  of  a 
short  piece  of  No.  12  copper  wire  to  ignite  the  charge  ; 
it  is  provided  with  a  valve  D  at  the  lower  end  to  pre- 
vent the  escape  of  the  enclosed  air." 

Manipulation. — One  gram  of  coal  ground  to  pass  a 
loo-mesh  sieve,  dried  at  105°,  is  put  into  the  cartridge, 
16-18  grams  of  sodium  peroxide  added,  the  top 
screwed  on,  and  the  whole  shaken  to  thoroughly  mix 
the  contents.  The  peroxide  should  be  fine  enough  to 
pass  a  25-mesh  sieve.  The  cartridge  is  tapped  to 
settle  the  charge  to  the  bottom,  placed  in  the  calor- 
imeter, two  liters  of  water  poured  in,  and  rotated  50 
to  100  revolutions  per  minute.  The  water  should  be 
3  to  4  degrees  lower  than  the  room  temperature. 
When  the  temperature  has  become  constant,  the 
thermometer  is  read,  a  hot  wire  dropped  down 
G,  igniting  the  charge,  which  burns  completely. 
The  extraction  of  the  heat  is  effected  in  about  five 
minutes;  the  reading  of  the  maximum  temperature 
is  taken  and  the  calculations  made  as  follows :  The 
rise  of  temperature  is  corrected,  first,  for  that  produced 
by  the  hot  wire;  this  amounts  to  0.006°  C.  per  i  inch 
of  No.  12  copper  wire:  second,  for  the  heat  produced 
by  the  combination  of  the  sodium  peroxide  with  the 
carbon  dioxide  and  water  formed  by  the  combus- 
tion ;  this  amounts  to  27  per  cent  of  the  total  indi- 
cated heat.  If  C  =  the  heat  of  combustion  of  the 
coal,  C'  the  calories  indicated,  t  the  rise  of  tempera- 
ture, and  w  the  water  employed,  then 


FUEL   ANALYSIS— HEATING    VALUE.  95 

c'  =  (t  -  0.006°)  x  w,   e  =  C'  - 

C  =  (/  —  0.006°)  X  w  X  0.73. 

Notes. — Instead  of  using  a  gram  of  coal  some  prefer 
to  use  half  this  quantity,  mixing  it  thoroughly  and 
rapidly  with  the  peroxide  in  a  watch-glass  with  a  spatula 
and  transferring  it  to  the  combustion-chamber. 

Ignition  by  an  electrically  heated  platinum  wire  is 
to  be  preferred  to  that  by  dropping  a  hot  copper  wire 
into  the  mixture.  Accidents  have  been  caused  from 
the  failure  of  the  valve  to  work. 

The  combustion-chamber  should  be  perfectly  dry 
within  and  without. 

Ashes  and  coke  are  difficult  of  ignition :  this  can  be 
effected  by  adding  a  second  charge  of  peroxide  with 
half  a  gram  of  good  coal,  the  combustion  factor  of 
which  has  been  determined,  and  thoroughly  mixing 
the  charges  and  repeating  the  ignition. 

For  stirring,  the  smallest  size  electric  or  water 
motor  furnishes  sufficient  power. 

In  the  formulae  w  =  the  water  employed  -|-  the 
water  equivalent  of  the  calorimeter. 

BertJiier' s  Method.  —  Another  method  of  direct 
determination  was  proposed  by  Berthier  in  1835.* 
It  uses  as  a  measure  of  the  heating  value  the  amount 
of  lead  which  a  fuel  would  reduce  from  the  oxide;  in 
other  words,  it  is  proportional  to  the  amount  of  oxygen 
absorbed. 

The  method  is  as  follows  f :   Mix  one  gram  of  the 

*  Dingler's  Polytechnisches  Journal,  58,  391. 

f  Noyes,  McTaggart  &  Graver,  J.  Am.  Chem.  Soc.,  17,  847  (1895). 


96  CAS  AND  FUEL   ANALYSIS. 

finely  powdered  dry  coal  with  60  grams  of  oxide  of 
lead  (litharge)  and  10  grams  of  ground  glass.  This 
mixing  can  be  done  with  a  palette-knife  on  a  sheet  of 
glazed  paper;  the  mixture  is  transferred  to  a  fire-clay 
crucible  (Battersea  C  size),  covered  with  salt,  the 
crucible  covered  and  heated  to  redness  in  a  hot  gas- 
furnace — or  the  hottest  part  of  the  boiler-furnace — for 
15-20  minutes.  After  cooling,  the  crucible  is  broken 
and  the  lead  button  carefully  cleaned  and  weighed. 
Multiply  the  weight  of  the  lead  button  obtained  by 
268.3  calories  (or  483  B.  T.  U.)  and  divide  the  prod- 
uct by  the  weight  of  coal  taken.  The  result  is  the 
number  of  calories  per  gram  or  B.  T.  U.  per  pound. 
One  gram  of  lead  is  theoretically  equivalent  to  234 
calories  (C) ;  owing  to  the  hydrogen  present  this  factor 
gives  results  about  two  per  cent  too  low.  The  results 
obtained  by  the  author  using  "  horn-pan  "  scales  in  one 
case  by  this  method  were  within  2.8  per  cent  of  those 
yielded  by  the  bomb  calorimeter,  which  are  as  close 
as  those  obtained  by  any  calorimeter  save  Parr's. 
The  method  would  seem  worthy  of  more  attention 
than  it  has  received. 


b.   Determination  of  Heating  Value  by  Calculation. 

The  method  of  determination  of  the  heating  value 
first  described,  though  exact,  has  the  disadvantages 
that  the  apparatus  is  costly  and  the  compressed 
oxygen  is  not  easily  obtained.  To  obviate  these, 
it  has  been  sought  to  obtain  the  heating  value  by 
calculation  from  the  chemical  analysis,  the  heating 
value  of  the  constituents  being  known.  This  has 
the  disadvantage  that  we  have  no  absolute  knowl- 


FUEL   ANALYSIS— HEATING  VALUE.  97 

edge — nay,  not  even  an  approximate  idea — as  to  how 
the  carbon,  hydrogen,  water,  and  sulphur  exist  in  the 
coal,  so  that  any  formula  must  of  necessity  be  quite 
removed  from  the  truth.  Dulong  was  the  first  to 
propose  the  method  by  calculation,  and  his  formula*  is 

Soooe  +  345  oo(//  —  •§<?) 


H  = 


IOO 


c,  h,  and  o  representing  the  percentages  of  carbon, 
hydrogen,  and  oxygen  in  the  coal. 

Many  modifications  of  this,  considering  the  water 
formed,  the  heat  of  vaporization  of  carbon,  or  the 
volatile  hydrocarbons,  have  been  proposed. 

Bunte  f  finds  that  the  following  formula  J  gives  results 
varying  from  -\-  2.8  to  —  3.7  per  cent: 

/         o\ 
8o8o^4-  28800 \h  —  -    4-  2500^  —  6oow 

\  o  / 

IOO 

s  and  w  represent  the  percentages  of  sulphur  and 
water  respectively.  It  is,  however,  inapplicable  to 
anthracite  coal.  It  would  scarcely  seem  that  the 
sulphur  would  be  worth  considering  unless  high,  one 
per  cent  affecting  the  result  but  0.3  per  cent. 
Mahler  employs  the  formula* 

8140*:+  34500/2  —  3000(0  -f.  n) 

IOO 

o  and  n  representing  oxygen  and  nitrogen,  and  states 
that  it  gives  results  within  3  per  cent. 

The  results  obtained  by  these  formulae  for  anthracite 
coal  are  as  a  rule  considerably  too  low. 

*  H  burned  to  liquid  water.         \  H  burned  to  aqueous  vapor, 
f  Jour,  fiir  Gasbalouehtung,  34,  21-2^  ?nr\  41-47. 


98  GAS  AND   FUEL   ANALYSIS. 

Goutal  *  has  proposed  the  formula 

8150^  +  AM 


p 


100 


as  being  more   readily  applicable  than  the  preceding. 
This  gives  the  results  in  calories. 

P  represents  the  calorific  power,  expressed  in  calories ; 
Cj  the  percentage  of  fixed  carbon  (coke  — ash);  M,  the 
percentage  of  volatile  matter  (100—  [coke  +  ash  + 
water]);  A  is  a  coefficient  which  varies  with  the  amount 
of  volatile  matter  M,  viz., 

M  =    2  to  15  A  =  13000 

1 5 'to  30  10000 

30  to  35  950° 

35  to  40  9000 

The  results  upon  a  series  of  American  coals  varied 
less  than  2  per  cent  from  those  obtained  by  the 
calorimeter.  It  is,  however,  only  applicable  to  high- 
grade  coals, 

REFERENCES. — An  admirable  discussion  of  the  errors 
incident  to  the  use  of  the  Mahler  calorimeter  and  others 
of  that  type  will  be  found  in  a  paper  by  G.  A.  Fries, 
Bulletin  No.  94  (1907),  U.  S.  Dept.  of  Agriculture, 
Bureau  of  Animal  Industry,  "Investigations  in  the  Use 
of  the  Bomb  Calorimeter." 

*  Revue  de  chimie  ind.,  7  (1896),  65;  abs.  in  The  Analyst,  24, 
107. 


FURL  ANALYSIS— HEATING  VALUE.  99 

CALORIFIC    POWER    OF    GASEOUS    FUEL. 

a.   Direct  Determination. 

Perhaps  the  best  apparatus  for  the  determination  of 
the  heating  value  of  gases  is  the  Junkers  calorimeter, 
Figs.  19  and  20.  The  following  description  is  taken 


FIG.  19. — JUNKERS  GAS-CALORIMETER  (SECTION). 

from  an  article  by  Kuhne  in  the  Journal  of  the  Society 
of  Chemical  Industry,   vol.    14,   p.  631.     As  will  be 


100  GAS  AND   FUEL  ANALYSIS. 

seen  from  Fig.  19,  this  consists  of  a  combustion-cham- 
ber, 28,  surrounded  by  a  water-jacket,  15  and  16, 
this  being  traversed  by  a  great  many  tubes.  To 
prevent  loss  by  radiation  this  water-jacket  is  sur- 


FIG.  20. — JUNKERS  GAS-CALORIMETER. 

rounded  by  a  closed  annular  air-space,  13,  in  which 
the  air  cannot  circulate.  The  whole  apparatus  is 
constructed  of  copper  as  thin  as  is  compatible  with 
strength.  The  water  enters  the  jacket  at  i,  passes 
down  through  3,  6,  and  7,  and  leaves  it  at  21,  while 


FUEL   ANALYSIS— HEATING 

the  hot  combustion-gases  enter  at  30  and  pass  down, 
leaving  at  31.  There  is  therefore  not  only  a  very 
large  surface  of  thin  copper  between  the  gases  and  the 
water,  but  the  two  move  in  opposite  directions,  during 
which  process  all  the  heat  generated  by  the  flame  is 
transferred  to  the  water,  and  the  waste  gases  leave  the 
apparatus  approximately  at  atmospheric  temperature. 
, The  gas  to  be  burned  is  first  passed  through  a  meter, 
Fig.  20,  and  then,  to  insure  constant  pressure,  through 
a  pressure-regulator.  The  source  of  heat  in  relation 
to  the  unit  of  heat  is  thus  rendered  stationary;  and  in 
order  to  make  the  absorbing  quantity  of  heat  also 
stationary,  two  overflows  are  provided  at  the  calo- 
rimeter, making  the  head  of  water  and  overflow  con- 
stant. The  temperatures  of  the  water  entering  and 
leaving  the  apparatus  can  be  read  by  12  and  43;  as 
shown  before,  the  quantities  of  heat  and  water  passed 
through  the  apparatus  are  constant.  As  soon  as  the 
flame  is  lighted,  43  will  rise  to  a  certain  point  and  will 
remain  nearly  constant. 

Manipulation. — The  calorimeter  is  placed  as  shown 
in  Fig.  20,  so  that  one  operator  can  simultaneously 
observe  the  two  thermometers  of  the  entering  and 
escaping  water,  the  index  of  the  gas-meter,  and  the 
measuring-glasses. 

No  draft  of  air  must  be  permitted,  to  strike  the  ex- 
haust of  the  spent  gas. 

The  water-supply  tube  w  is  connected  with  the 
nipple  a  in  the  centre  of  the  upper  container;  the 
other  nipple,  b,  is  provided  with  a  waste-tube  to  carry 
away  the  overflow,  which  latter  must  be  kept  running 
while  the  readings  are  taken. 


T02  ;  .  tA£  AND    FUEL  ANALYSIS. 

The  nipple  c  through  which  the  heated  water  leaves 
the  calorimeter  is  connected  by  a  rubber  tube  with 
the  large  graduate,  d  empties  the  condensed  water 
into  the  small  graduate. 

The  thermometers  being  held  in  position  by  rubber 
stoppers  and  the  water  turned  on  by  e  until  it  dis- 
charges at  c,  no  water  must  issue  from  d  or  from  39, 
Fig.  19,  as  this  would  indicate  a  leak  in  the  calorim- 
eter. 

The  cock  e  is  now  set  to  allow  about  two  liters  of 
water  to  pass  in  a  minute  and  a  half,  and  the  gas 
issuing  from  the  burner  ignited.  Sufficient  time  is 
allowed  until  the  temperature  of  the  inlet-water 
becomes  constant  and  the  outlet  approximately  so; 
the  temperature  of  the  inlet-water  is  noted,  the  read- 
ing of  the  gas-meter  taken,  and  at  this  same  time  the 
outlet-tube  changed  from  the  funnel  to  the  graduate. 
Ten  successive  readings  of  the  outflowing  water  are 
taken  while  the  graduate  (2-liter)  is  being  filled  and 
the  gas  shut  off. 

A  better  procedure  is  to  allow  the  water  to  run  into 
tared  8-liter  bottles,  three   being  used  for  a   test,  and 
weighing  the  water.      The   thermometer  in  the  outlet 
can  then  be  read  every  half-minute. 
EXAMPLE. — Temp,  of  incoming  water,  17.2° 
"       "  outgoing       "        43.8° 

Increase,  26.6° 

Gas  burned,  0.35  cu.  ft. 

„         _  liters  water  X  increase  of  temp.  _  2  X  26.6 
cu.  ft.  gas  0.35 

=  152  3C. 

From  burning  one  cubic  foot  of  gas  27.25  cc.  of 
water  were  condensed.  This  gives  off  on  an  average 
0.6  C.  per  cc. 


FUEL  ANALYSTS — HEATING    VALUE.  103 

27.25  xo.6=  16.3  C;  152.3  —  16.3=  136  C.  per  cubic 
foot;  136x3-96823  =  540  B.  T.  U. 

The  calorific  power  obtained  without  subtracting 
the  heat  given  off  by  the  condensation  of  the  water 
represents  the  total  heating  value  of  the  gas.  This  is 
the  heat  given  off  when  the  gas  is  used  for  heating 
water  or  in  any  operation  where  the  products  of 
combustion  pass  off  below  100°  C.  The  net  heating 
value  represents  the  conditions  in  which  by  far  the 
greater  quantity  of  gas  is  consumed,  for  cooking, 
heating  and  gas  engines,  and  is  the  one  which  should 
be  reported.  It  should,  however,  be  corrected,*  as 
shown  on  page  106,  to  the  legal  cubic  foot,  that  is, 
measured  at  30  inches  barometric  pressure,  and  60° 
F.  saturated  with  moisture. 

The  apparatus  has  been  tested  for  three  months 
in  the  German  Physical  Technical  Institute  with  hy- 
drogen, with  but  a  deviation  of  0.3  per  cent  from 
Thomson's  value.  This  value  may  vary  nearly  that 
amount  from  the  real  value  owing  to  the  method 
which  he  employed. 

b.  By  Calculation. 

Oftentimes  it  may  be  impracticable  to  determine 
the  heating   value   of    gases  directly;    in   such   cases, 
recourse  must  be  had  to  the  calculation  of  its  calorific 
power  from  volumetric  analysis  of  the  gas. 

To  this  end  multiply  the  percentage  of  each  con- 
stituent by  its  number  as  given  in  Table  IV,  and  the 
sum  of  the  products  will  represent  the  British  Thermal 
Units  evolved  by  the  combustion  of  one  cubic  foot  of 

*  A  difference  of  i°  C.  or  of  3  mm.  pressure  makes  a  change  of  0.3 
per  cent  in  the  volume.  Pfeiffe,  J.  Gasbeleucht.  50,  67  (1907). 


104  GAS  AND  FUEL   ANALYSIS. 

the  gas.*  It  is  assumed  that  the  temperature  of  the 
gas  burned  and  the  air  for  combustion  is  60°  F.,  and 
that  of  the  escaping  gases  is  328°  F.,  that  correspond- 
ing to  the  temperature  of  steam  at  100  pounds  abso- 
lute pressure. 

As  has  been  already  stated,  column  3  in  Table  IV 
is  based  upon  the  assumption  that  the  gas,  and  air  for 
its  combustion,  enter  at  60°  F.,  and  the  products 
of  combustion  leave  at  328°  F. ;  in  column  4  it  is 
assumed  that  the  entering  temperature  of  both  gas 
and  air  is  32°  F.,  and  the  combustion-gases  are  cooled 
to  32°  F.  In  case  these  conditions  are  varied,  the 
amount  of  heat  which  the  gas  and  air  bring  in  must  be 
determined;  this  is  found  in  the  usual  way  by  multi- 
plying the  proportionate  parts  of  I  cubic  foot,  as 
shown  by  the  analysis,  by  the  specific  heat  of  the  gas, 
and  this  by  the  rise  in  temperature  (difference  between 
observed  temperature  and  32°  F.).  The  quantity  of 
air  necessary  for  combustion  is  found  by  multiplying 
the  percentage  composition  of  the  gas  by  the  number 
of  cubic  feet  necessary  for  the  combustion  of  each 
constituent. 

An  example  will  serve  to  make  this  clear.  The 
analysis  of  Boston  gas  is  as  follows:* 

CO3      "  Illuminams."  O  CO          CH4  H  N 

2.9  15.0  o.o         25.3         25.9         27.9         3.0 

Or  in  one  cubic  foot  there  are 

*  H.  L.  Payne,  Jour.  Analytical  and  Applied  Chem.,  7,  230. 
f  Jenkins,  Annual  Report  Inspector  of  Gas  Meters  and  Illuminating 
Gas,  1896,  p.  ii. 


FUEL    ANALYSIS— HEATING  VALUE.  105 

.029  CO3 259  CH4 

.150  "  illuminants  " 279  H 

.253  CO., 030  N 

Let  us  assume  that  the  gases,  instead  of  passing 
out  at  a  temperature  of  328°  F.,  leave  at  the  same 
temperature  as  that  of  the  chimney-gases,  p.  29,  250° 
C.  or  482°  F. 

The  calculation  of  the  heat  carried  away  is  similar 
to  that  there  given. 
0.15    cu,   ft.  of  "  illuminants  "  produces,  Table   III, 

0.3  cu.  ft.  CO2  and  0.3  cu.  ft.  steam; 
0.253  cu.  ft.  of   carbonic   oxide  produces  .253  cu.  ft. 

C02; 
0.259  cu.  ft.  methane  produces  0.259  cu-  ^-  CO2  and 

.518  cu  ft.  steam ; 
0.279  cu-  ft-  hydrogen  produces  .279  cu.  ft.  steam. 

From  the  combustion  of  the  gas  there  results  .812 
cu.  ft.  CO2 ,  1.097  cu.  ft.  steam,  and  5.90  X  79.08  or 
4.665  cu.  ft.  N. 

The  quantity  of  heat  they  carry  off  is  as  follows: 

Vol.  Vol.  Sp.  Ht.  Rise.  B.T.U. 

CO2 812  X  .027     X    450=  9.9 

N 4.66    X  .019    X    45°=  39-9 

Excess  of  air. .    1.2       X  .019    X     450  =  10.2 

Steam.,. 1>Q97  X  .0502  X  1229  =  67.7 


Total  heat  lost. =     127.7 


106  GAS  AND  FUEL  ANALYSIS. 

The  loss  due  to  the  steam  is  found  by  multiplying 
the  weight  of  steam  found  by  the  "  Total  Heat  of 
Steam,"  as  found  from  Steam  Tables.*  The  tables, 
however,  do  not  extend  be)'ond  428°  F. ;  it  can  be 
calculated  by  the  formula 

Total  heat  —  A  =  1091.7  +  o.3O5(/  —  32). 

One  cubic  foot  of  hydrogen  when  burned  yields 
.0502  Ibs.  of  water. 

The  heat  generated  by  the  combustion  of  the  gas  is 
found  by  multiplying  its  volume  by  its  calorific  power, 
Table  IV. 

"  Illuminants" 0.15     X  2000.0  =  300.0  B.T.U. 

CO Q253X     341-2=    86.3 

CH4 0.259  X  1065.4=276.0 

H 0.279  X     345-4=    96-3 


Heat  generated  by  the  gas 75^.6  B.T.U. 

Total  heat  lost  (p.  98) 127.7 

630.9  B.T.U. 

This  figure,  630.9  B.T.U.,  represents  the  heating 
power  of  one  cubic  foot  of  the  gas  measured  at  62°  F., 
and  is  consequently  too  small ;  its  heating  value  at 
32°  F.  is  represented  by 

492  +  3-  X  630.9,  or  669. 1  B.T.U. 
492 

The  above  calculation,  like  all  givmg  accurate  results, 
is  somewhat  tedious;  a  shorter  and  less  correct  one  is  as 
follows:  Divide  the  figures  found  in  the  last  column  of 

*  Peabody's  Steam  Tables. 


FUEL    ANALYSIS— HEATING    VALUE.  107 

Table  IV  of  the  Appendix  by  100,  the  result  gives  the 
heating  value  of  these  gases  in  B.T.U.  per  cubic  centi- 
meter.* According  to  the  volumetric  analysis  of  the 
gas  there  are  in  IQO  cc.  the  following: 

15.0  cc.  illuminants,         25.3  cc.  carbonic  oxide; 
29.5  cc.  methane,  27.9  cc.  hydrogen; 

the  heating  value  is 

15.0X20.0  =300.0  B.T.U. 

25. 3X  3.41=  86.3 
25.9X10.65  =  276.0 
27. 9X  3-45=  96-3 


758. 6  B.T.U. 

the  same  as  the  gross  heating  value  obtained  by  the  other 
method.     No  correction  is  applied  for  the  heat  lost. 


*  Method  followed  in  Prof.  Paper,  No.  48,   U.   S.   Geol.   Survey, 
Part  III,  p.  1005. 


APPENDIX. 


TABLE   I. 

TABLE  SHOWING  THE  TENSION  OF  AQUEOUS  VAPOR  AND  ALSO  THE 
WEIGHT  IN  GRAMS  CONTAINED  IN  A  CUBIC  METER  OF  AIR 
WHEN  SATURATED. 

From  5°  to  30°  C. 


Temp. 

Tension, 
mni. 

Grams. 

Temp. 

Tension, 
mm. 

Grams. 

Temp. 

Tension, 
mm. 

Grams. 

5 

6-5 

6.8 

14 

II.  9 

12.0 

23 

20.9 

20.4 

6 

7.0 

7-3 

15 

12-7 

12.8 

24 

22.2 

21-5 

7 

7-5 

7-7 

16 

13-5 

13-6 

25 

23.6 

22-9 

8 

8.0 

8.1 

17 

14.4 

14-5 

26 

25.0 

24.2 

9 

8-5 

8.8 

18 

15-4 

I5-I 

27 

26.5 

25.6 

10 

9.1 

9.4 

19 

I6.3 

16.2 

28 

28.1 

27.0 

ir 

9.8 

IO.O 

20 

17.4 

17.2 

29 

29.8 

28.6 

12 

10.4 

10.6 

21 

18-5 

18.2 

30 

31-5 

29.2 

13 

n.  i 

n-3 

22 

19.7 

19-3 

TABLE    II. 

"VOLUMETRIC"  SPECIFIC  HEATS  OF  GASES.* 


Air 0.019 

Carbon  dioxide 0.027 

Carbonic  oxide 0.019 

Hydrogen 0.019 


"  Illuminants  " 0.040 

Methane 0.027 

Nitrogen 0.019 

Oxygen 0.019 


The  "volumetric"  specific  heat  is  the  quantity  of  heat  neces- 
sary to  raise  the  temperature  of  one  cubic  foot  of  gas -from  32°  F. 
to  33°  F. 


*  H.  L.  Payne,  Jour.  Anal,  and  Applied  Chem.,  7,  233. 

109 


.  10  APPENDIX, 

TABLE  III. 

THE  VOLUME  OF  OXYGEN  AND  AIR  NECESSARY  TO  BURN  ONE  CUBIC 
FOOT  OF  CERTAIN  GASES,  TOGETHER  WITH  THE  VOLUME  OF  THE 
PRODUCTS  OF  COMBUSTION. 


Name. 

Formula. 

Volume 
of 
Oxygen. 

Volume* 
of 
Air. 

Volume 
of 
Steam. 

Volume 
of  Carbon 
Dioxide. 

Ignition 
Point 
Deg  P. 

Hydrogen  .... 
Carbonic  oxide 
Methane  
Ethane  
Propane. 

H2 
CO 
CH4 
C2H6 
C3H8 

°-5 
0-5 
2.O 

3-5 

e    o 

2-39 
2-39 
9.56 
16.73 

27     QO 

I 
O 
2 

3 

0 

I 
I 
2 

-2 

1085  II 
1200  || 
1230 
II4O 
IOI  ^ 

Butane  
Pentane. 

C4H10 
C5Hi2 

6-5 

8  o 

31.07 

?8    24. 

5 
6 

4 

c 

Hexane  ..'.... 

C6Hi4 

9-5 

45  -41 

7 

6 

1400 

Ethylenef  .... 
Propylenef.  .  . 
Benzene  §  

C2H4 
CsHe 
C6H6 

3-0 
4-5 
7    5 

14-34 
21.51 
35  8q 

2 

3 

•2 

2 

3 
6 

ioio|| 

940 

Acetylene.  .  .  . 

C2H2 

2-5 

n-95 

I 

2 

788  II 

*Air   being    20.92    per    cent    by  .volume,    4.78    volumes    contain 
i  volume  of  oxygen.- 

t  The  chief  constituent  of  "illuminants,"  new  name  "ethene." 
t  New  name  "propene." 

§  Often  called  benzol,  not  to  be  confounded  with  benzme. 
||  Dixon  &  Coward,  Proc.  Chem.  Soc.,  26,  67. 


TABLES. 


Ill 


TABLE    IV. 

CALORIFIC    POWER    OF    VARIOUS    GASES*  IN    BRITISH    THERMAL    UNITS 
PER    CUBIC    FOOT. 


Name. 

Symbol. 

60°  initial. 
328°  Hual.§ 

32°  initial. 
32°  final. 

1  1  vdrofifen    

H 

263    2 

O/1  C       A 

Ccirboni  *  oxide  

CO 

qob    Q 

o/i  T    o 

M  ethane  

CH4 

853  o 

1065  o 

J  11  u  rnijiantsf  

I  7OO  .  O 

2OOO   O 

Ethane 

C.,H« 

1861  o 

CsHs 

Butane-.  

C4HIO 

'I  A  J  I  .  O 

Pentanf* 

r.H.o 

H  exanei 

C6H  4 

5O1  7    O 

Ethyl°ne    •  . 

C2H4 

i6?j.  o 

Propyleue 

C3H6 

OCOQ    O 

Benzene  

CfiHe 

4012  o 

Acetylene      .           

C2H2 

1477  o 

*  H.  L.  Payne,  loc.  cil. 

f  Where  the  "illuminants"  are  derived  chiefly  from  the  decom- 
position of  mineral  oil. 

|The  chief  constituent  of  the  "gasolene"  used  in  the  gas  machines 
for  carburelting  air. 

§  The  temperature  of  steam  at  100  Ibs.  absolute  pressure. 

TABLE  V. 

CALORIFIC  POWER  OF  VARIOUS  LIQUIDS  IN  BRITISH  THERMAL  UNITS  PER 

POUND. 


Name. 

B.  T.  U. 

Pounds  of  Air  for 
Combustion. 

Crude  petroleum  Lima  Ohio 

20,890 

Crude  petroleum.  Oil  Creek,  Pa  
Crude  petroleum,  heavy,  W.  Va  
63°  Be.  gasolene                        .        .... 

21,600 
18,180 
19,162-20,448 

14  96* 

114°  F.  flash  kerosene          

18,643-19,892 

14.89* 

1  50°  fire-test  kerosene  

18,290 

Mineral  sperm  

20,065 

Ethyl  alcohol,  Q5  per  cent  

10,504 

Methyl  alcohol 

Q,C6S 

Denatured  alcohol 

IO,5l2—II,6l6 

8   is* 

*  Bull/43  Bureau  of  Mines,"i9i2,  pp.  18-21.  "Fuel  Values^of  Gasolene 
and  Denatured  Alcohol  in  Internal  Combustion  Engines."^ 


112 


APPENDIX. 


TABLE  VI. 

CALORIFIC  POWER  OF  CERTAIN  SOLID  FUELS  IN  BRITISH  THERMAL  UNITS 
PER  POUND,  FIGURED  ON  THE  PURE  DRY  COMBUSTIBLE. 

Anthracite 13,740-15,620 

Bituminous  coal: 

Cumberland 16,320 

Georges  Creek 15,140 

Pocahontas 15,700 

West  Virginia 13,700 

Brown  coal 9,060-14,240 

Coke 13,880-14,560 

Peat 7,400-10,625 

Tanbark 6,100 

Wheat  straw 10,380 

Wood,  hard 8,500 

Wood,  pine 9j*5o 


TABLE  VII. 

SHOWING  THE  WEIGHT  OF  A  LITER  AND  SPECIFIC  GRAVITY  REFERRED 
TO    AIR,    OF    CERTAIN    GASES  AT    O°    C.    AND    760    MM. 


Name  of  Gas. 

Weight,  Grams. 

Specific  Gravity. 

i  .  z^i 

.907 

Hydrogen    ....        .                . 

•  t^y 

Methane  

Nitrogen  

I    2^H 

I    A^O 

I    IO5 

Air  

I  .  2QJ. 

I    OOO 

TABLES.  113 

TABLE  VIII. 

SOLUBILITY    OF    VARIOUS    GASES    IN    WATER. 

One  volume  of  water  at  20°  C.  absorbs  the  following  volumes  of 
gas  reduced  to  o°  C.  and  760  mm.  pressure. 


Name  of  Gas. 

Symbol. 

Volumes. 

CO 
C03 

H2 
CH4 

N2 
02 

0.023 
O.QOI 
0.019 
0.035 
0.014 
0.028 
0.017 

Air  

TABLE  IX. 

MELTING-POINTS    OF    VARIOUS    METALS    AND    SALTS,    FOR    USE    WITH 
APPARATUS    FIG.    II. 


Alphabetically. 

Aluminium 658°  C. 

Antimony 630 

fBarium  chloride 950 

Bismuth 270 

Calcium  fluoride 902 

Cadmium 302 

fCadmium  chloride 541 

Copper 1083 

Lead. 327 

fPotassium  bromide.  . .  .  740 

t  Potassium  chloride ....  780 

fSodium  bromide 748 

fSodium  carbonate 853 

Tin 232 

Zinc 419 


By  Temperatures. 

Tin 232°  C.* 

Bismuth 270* 

Cadmium 302* 

Lead 327* 

Zinc 419* 

Cadmium  chloride 54iJ 

Antimony 630* 

Aluminium 658* 

Potassium  bromide 74O* 

Sodium  bromide 748* 

Potassium  chloride 780* 

Sodium  carbonate 853* 

Calcium  fluoride 902  § 

Barium  chloride 950* 

Copper 1083* 


*  Burgess-Le  Chatelier,  Measurement  of  High  Temperatures,  1912. 
f  These  salts  must  be  dried  at  105°  C.  to  a  constant  weight. 
J  Carnelley,  Melting-  and  Boiling-point  Tables. 
§  Meyer,  Riddle  and  Lamb,  Ber.  d.  deut.  Chem.  Gesellsch.,  27, 
3140  (1894). 


H4 


APPENDIX. 
TABLE  X. 


GIVING    THE    NUMBER     OF     TIMES     THE    THEORETICAL    QUANTITY    OF 
AIR    SUPPLIED,    WITH    VARIOUS    GAS    ANALYSES.* 


C02  + 

co. 

N  =  70. 
C02+0+CO  =  2i 

N  =  8o. 
CO2-!-O+CO=2o. 

N  =  81. 
CO2+O+CO=i9. 

N  =  82. 
CO2+O+CO  =  i8. 

21 

.OO 

.    .    .    4 

20 

•05 

.00 

.... 

.... 

I) 

.10 

•05 

.00 

.... 

18 

•  17 

.  IO 

.05. 

.OO 

1.7 

•23 

.16 

.  IO 

•05 

16 

•  31 

•23 

.16 

.10 

15 

.40 

•3i 

•23 

.16 

14 

•  50 

•39 

•30 

.22 

13 

.61 

•49 

•39 

•30 

12 

•75 

.60 

.48 

.38 

II 

.91 

•73 

•59 

•47 

IO 

2.10 

.89 

•72 

•58 

9 

2-33 

2.07 

.87 

.70 

8 

2.62 

2.29 

2.04 

1.85 

7 

3.00 

2-57 

2.26 

2.  02 

6 

3-50 

2.92 

2.52 

2.23 

5 

4.20 

3-39 

2.86 

2.48 

4 

5-25 

4.05 

3-30 

2-79 

3 

7.00 

5-oo 

3-89 

3-20 

2 

10.50 

6-53 

4-76 

3.76 

I 

21  .00 

9-43 

6.10 

4-54 

*  Coxe,  Proc.  N.  E.  Cotton  Manufacturers'  Assoc.,  1895. 


TABLE    XI. 

COMPARISON   OF   METRIC   AND    ENGLISH    SYSTEMS, 

I  cubic  inch  =  16.39  c.c. 

I  cubic  foot  =  28.315  liters. 

I  Imperial  gallon  =    4.543      " 


I  Ib.  avoirdupois  =  453-593  grams. 

I  calorie  =      3.969  B.T.U.  (Rontgen). 


COAL   AND  FUEL  OIL  SPECIFICATIONS.  115 


COAL   AND   FUEL   OIL  SPECIFICATIONS. 

COAL  SPECIFICATIONS. 

The  following,  from  Bulletin  339,  U.  S.  Geological  Survey  (1908),  by 
D.  T.  Randall,  will  give  an  idea  of  some  coal  specifications: 

SPECIFICATIONS  FOR  THE  U.  S.  GOVERNMENT  FUEL 
SUPPLY  AS  APPROVED  BY  THE  NATIONAL  ADVISORY 
BOARD  ON  FUELS  AND  STRUCTURAL  MATERIALS, 
MARCH,  1907. 

SPECIFICATIONS  AND  PROPOSALS  FOR  SUPPLYING  COAL. 

United  States 

,19° 

PROPOSAL. 

Sealed  proposals  will  be  received  at  this  office  until  2  o'clock  P.M., 

190.  .,  for  supplying  coal  to  the  United  States building 

at as  follows: 


The  quantity  of  coal  stated  above  is  based  upon  the  previous  annual 
consumption,  and  proposals  must  be  made  upon  the  basis  of  a  delivery 
of  10  per  cent  more  or  less  than  this  amount,  subject  to  the  actual 
requirements  of  the  service. 

Proposals  must  be  made  on  this  form,  and  include  all  expenses 
incident  to  the  delivery  and  stowage  of  the  coal,  which  must  be  delivered 
in  such  quantities  and  at  such  times  within  the  fiscal  year  ending 
June  30,  190. .,  as  may  be  required. 

Proposals  must  be  accompanied  by  a  deposit  (certified  check,  when 

practicable,  in  favor  of )  amounting  to  10  per  cent 

of  the  aggregate  amount  of  the  bid  submitted,  as  a  guaranty  that  it  is 
bona  fide.  Deposits  will  be  returned  to  unsuccessful  bidders  imme- 
diately after  award  has  been  made,  but  the  deposit  of  the  successful 
bidder  will  be  retained  until  after  the  coal  shall  have  been  delivered 
and  final  settlement  made  therefor,  as  security  for  the  faithful  per- 
formance of  the  terms  of  the  contract,  with  the  understanding  that 
the  whole  or  a  part  thereof  may  be  used  to  liquidate  the  value  of  any 


Ti6  APPENDIX. 

deficiencies  in  quality  or  delivery  that  may  arise  under  the  terms  of 
the  contract. 

When  the  amount  of  the  contract  exceeds  $10,000,  a  bond  may  be 
executed  in  the  sum  of  25  per  cent  of  the  contract  amount,  and  in  this 
case  the  deposit  or  certified  check  submitted  with  the  proposal  will 
be  returned  after  approval  of  the  bond. 

The  bids  will  be  opened  in  the  presence  of  the  bidders,  their  repre- 
sentatives, or  such  of  them  as  may  attend,  at  the  time  and  place  above 
specified. 

In  determining  the  award  of  the  contract,  consideration  will  be 
given  to  the  quality  of  the  coal  offered  by  the  bidder,  as  well  as  the 
price  per  ton,  and  should  it  appear  to  the  best  interests  of  the  Govern- 
ment to  award  the  contract  for  supplying  coal  at  a  price  higher  than 
that  named  in  lower  bid  or  bids  received,  the  award  will  be  so  made. 

The  right  to  reject  any  or  all  bids  and  to  waive  defects  is  expressly 
reserved  by  the  Government. 

DESCRIPTION  OF  COAL  DESIRED.* 

Bids  are  desired  on  coal  described  as  follows: 


Coals  containing  more  than  the  following  percentages,  based  upon 
dry  coal,  will  not  be  considered: 

Ash per  cent 

Volatile  matter per  cent 

Sulphur per  cent 

Dust    and   fine   coal   as   delivered   at   point   of 

consumption  f per  cent 

DELIVERY 

The  coal  shall  be  delivered  in  such  quantities  and  at  such  times  as 
the  Government  may  direct. 

In  this  connection  it  may  be  stated  that  all  the  available  storage 
capacity  of  the  coal  bunkers  will  be  placed  at  the  disposal  of  the  con- 
tractor to  facilitate  delivery  of  coal  under  favorable  conditions. 

*  This  information  will  be  given  by  the  Government  as  may  be  determined 
by  boiler  and  furnace  equipment,  operating  conditions,  and  the  local    market. 
t  All  coal  which  will  pass  through  a  J-inch  round-hole  screen. 


COAL   AND   FUEL   OIL  SPECIFICATIONS.          117 

After  verbal  or  written  notice  has  been  given  to  deliver  coal  under 
this  contract,  a  further  notice  may  be  served  in  writing  upon  the  con- 
tractor to  make  delivery  of  the  coal  so  ordered  within  twenty-four 
hours  after  receipt  of  said  second  notice. 

Should  the  contractor,  for  any  reason,  fail  to  comply  with  the  second 
request,  the  Government  will  be  at  liberty  to  buy  coal  in  the  open 
market,  and  to  charge  against  the  contractor  any  excess  in  price  of 
coal  so  purchased  over  the  contract  price. 

SAMPLING. 

Samples  of  the  coal  delivered  will  be  taken  by  a  representative  of 
the  Government. 

In  all  cases  where  it  is  practicable,  the  coal  will  be  sampled  at  the 
time  it  is  being  delivered  to  the  building.  In  case  of  small  deliveries, 
it  may  be  necessary  to  take  these  samples  from  the  yards  or  bins.  The 
sample  taken  will  in  no  case  be  less  than  the  total  of  100  Ibs.,  to  be 
selected  proportionally  from  the  lumps  and  fine  coal,  in  order  that 
it  will  in  every  respect  truly  represent  the  quantity  of  coal  under  con- 
sideration. 

In  order  to  minimize  the  loss  in  the  original  moisture  content  the 
gross  sample  will  be  pulverized  as  rapidly  as  possible  until  none  of 
the  fragments  exceed  one-half  inch  in  diameter.  The  fine  coal  will 
then  be  mixed  thoroughly  and  divided  into  four  equal  parts.  Opposite 
quarters  will  be  thrown  out,  and  the  remaining  portions  thoroughly 
mixed  and  again  quartered,  throwing  out  opposite  quarters  as  before. 
This  process  will  be  continued  as  rapidly  as  possible  until  the  final 
sample  is  reduced  to  such  amount  that  all  of  the  final  sample  thus 
obtained  will  be  contained  in  the  shipping  can  or  jar  and  sealed  air- 
tight. 

The  sample  will  then  be  forwarded  to 

If  desired  by  the  coal  contractor,  permission  will  be  given  to  him, 
or  his  representative,  to  be  present  and  witness  the  quartering  and 
preparation  of  the  final  sample  to  be  forwarded  to  the  Government 
laboratories. 

Immediately  on  receipt  of  the  sample,  it  will  be  analyzed  and  tested 
by  the  Government,  following  the  method  adopted  by  the  American 
Chemical  Society,  and  using  a  bomb  calorimeter.  A  copy  of  the  result 
will  be  mailed  to  the  contractor  upon  the  completion  thereof. 


n8  APPENDIX. 


CAUSES  FOR  REJECTION. 

A  contract  entered  into  under  the  terms  of  this  specification  shall 
not  be  binding  if,  as  the  result  of  a  practical  service  test  of  reasonable 
duration,  the  coal  fails  to  give  satisfactory  results  owing  to  excessive 
clinkering  or  to  a  prohibitive  amount  of  smoke. 

It  is  understood  that  the  coal  delivered  during  the  year  will  be  of 
the  same  character  as  that  specified  by  the  contractor.  It  should, 
therefore,  be  supplied,  as  nearly  as  possible,  from  the  same  mine  or 
group  of  mines. 

Coal  containing  percentages  of  volatile  matter,  sulphur,  and  dust 
higher  than  the  limits  indicated  on  page  2  and  coal  containing  a  per- 
centage of  ash  in  excess  of  the  maximum  limits  indicated  in  the  follow- 
ing table  will  be  subject  to  rejection. 

In  the  case  of  coal  which  has  been  delivered  and  used  for  trial,  or 
which  has  been  consumed  or  remains  on  the  premises  at  the  time  of 
the  determination  of  its  quality,  payment  will  be  made  therefor  at  a 
reduced  price,  computed  under  the  terms  of  this  specification. 

Occasional  deliveries  containing  ash  up  to  the  precentage  indicated 
in  the  column  of  "Maximum  limits  for  ash,"  on  page  4,  may  be 
accepted.  Frequent  or  continued  failure  to  maintain  the  standard 
established  by  the  contractor,  however,  will  be  considered  sufficient 
cause  for  cancellation  of  the  contract. 

PRICE  AND  PAYMENT.* 

Payment  will  be  made  on  the  basis  of  the  price  named  in  the  pro- 
posal for  the  coal  specified  therein,  corrected  for  variations  in  heating 
value  and  ash,  as  shown  by  analysis,  above  and  below  the  standard 
established  by  contractor  in  this  proposal.  For  example,  if  the  coal 
contains  2  per  cent,  more  or  less,  British  thermal  units  than  the  estab- 
lished standard,  the  price  will  be  increased  or  decreased  2  per  cent 
accordingly. 

The  price  will  also  be  further  corrected  for  the  percentages  of  ash. 
For  all  coal  which  by  analysis  contains  less  ash  than  that  established 

*  The  economic  value  of  a  fuel  is  affected  by  the  actual  amount  of  com- 
bustible matter  it  contains,  as  determined  by  its  heating  value  shown  in  British 
thermal  units  per  pound  of  fuel,  and  also  by  other  factors,  among  which  is  its 
ash  content.  The  ash  content  not  only  lowers  the  heating  value  and  decreases 
the  capacity  of  the  furnace,  but  also  materially  increases  the  cost  of  handling 
the  coal,  the  labor  of  firing,  and  the  cost  of  removal  of  ashes,  etc. 


COAL    AND   FUEL  OIL  SPECIFICATIONS. 


in  this  proposal  a  premium  of  i  per  cent  per  ton  for  each  whole  per 
cent  less  ash  will  be  paid.  An  increase  in  the  ash  content  of  2  per  cent 
over  the  standard  established  by  contractor  will  be  tolerated  without 
exacting  a  penalty  for  the  excess  of  ash.  When  such  excess  exceeds 
2  per  cent  above  the  standard  established,  deductions  will  be  made 
from  the  price  paid  per  ton  in  accordance  with  following  table: 


jgco 

Cents  per  Ton  to  be  Deducted. 

a 

Ash  as     '•£  g 

3^ 

Establish-  3"j  £ 

g< 

ed  in  Pro-  *$     ,° 

2 

4 

7 

12 

18 

25 

35 

3    IH 

posaKPerp  ££ 

^ 

Cent). 

M     M 

55 

Percentages  of  Ash  in  Dry  Coal. 

S" 

5 

7 

7-  8 

8-9 

9-10 

IO-II 

11-12 

12-13 

13-14 

12 

6 

8 

8-  9 

9-10 

IO-II 

11-12 

12-13 

13-14 

14-15 

13 

7 

9 

9-10 

10-11 

11-12 

12-13 

13-14 

14-15 

15-16 

14 

8 

10 

IO-II 

11-12 

12-13 

13-14 

14-15 

15-16 

16-17 

14 

9 

ii 

11-12 

12-13 

13-14 

14-15 

15-16 

16-17 

17-18 

15 

10 

12 

12-13 

I3~I4 

14-15 

I5-I6 

16-17 

I7-I8 

16 

ii 

17 

14-15 

15-16 

16-17 

17-18 

I8-I9 

16 

12 

14 

I4-I  5 

i  ^—  16 

16—17 

17-18 

l8-I9 

I9-2O 

17 

13 

15 

15-16 

16-17 

17-18 

18-19 

I9-2O 

2O-2I 

18 

14 

16 

16-17 

17-18 

18-19 

I9-2O 

2O-2I 

21-22 

19 

15 

17 

I7-I8 

18-19 

IQ—  2O 

2O-2I 

21-22 

JQ 

16 

18 

18-19 

19—20 

2O—  21 

21  —  22 

22—23 

2O 

17 

10 

io—  20 

2O—  21 

21—22 

22—2^ 

21 

18 

20 

2O-2I 

21-22 

22-23 

22 

Proposals   to  receive   consideration  must  be   submitted   upon   this 
form  and  contain  all  of  the  information  requested. 


,  19°- • 

The  undersigned  hereby  agree  to  furnish  to  the  U.  S 

building  at  ,  the  coal  described,  in  tons  of  2,240  Ibs. 

each  and  in  quantity  10  per  cent  more  or  less  than  that  stated  on 
page  i,  as  may  be  required  during  the  fiscal  year  ending  June  30, 
190.  .,  in  strict  accordance  with  this  specification;  the  coal  to  be  de- 
livered in  such  quantities  and  at  such  times  as  the  Government  may 
direct. 


120 


APPENDIX. 


Item  No.  .  . 

Item  No.  .  . 

Item  No  ... 

Description. 

Location  of  mine  
Name  of  coal  bed 

Size    of    coal    (if    coal    is 
screened)  : 
Coal    to    pass   through 

inches  i  round 

inches  ~i  round 

Coal  to  pass  over  open- 
ings   

Data  to  establish  a  basis  for 
payment. 
Per  cent  of  ash  in  dry  coal 
(method    of    American 
Chemical  Society) 

|  square 
.  inches  J  bar 

square 
.  .inches    bar 

}  square 
.  .  inches  J  bar 

British   thermal   units   in 
coal  as  delivered 

Price  per  ton  (2,240  Ibs.)  .  . 

It  is  important  that  the  above  information  does  not  establish  a  higher 
standard  than  can  be  actually  maintained  under  the  terms  of  the  contract; 
and  in  this  connection  it  should  be  noted  that  the  small  samples  taken  from 
the  mine  are  invariably  of  higher  quality  than  the  coal  actually  delivered 
therefrom.  It  is  evident,  therefore,  that  it  will  be  to  the  best  interests  of  the 
contractor  to  furnish  a  correct  description  with  average  values  of  the  coal 
offered,  as  a  failure  to  maintain  the  standard  established  by  contractor  will 
result  in  deductions  from  the  contract  price,  and  may  cause  a  cancellation  of 
the  contract,  while  deliveries  of  a  coal  of  higher  grade  than  quoted  will  be 
paid  for  at  an  increased  price. 


Signature.  .  . 
Address . 


Name  of  corporation 

Name  of  president 

Name  of  secretary 

Under  what  law  (State)  corporation  is  organized , 


As  will  be  seen  from  the  foregoing  specification,  the  bidder  is  not 
required  to  submit  a  sample  of  his  coal,  but  is  expected  to  name  a 
standard  of  British  thermal  units  in  the  coal  as  it  is  to  be  delivered. 
This  value  is  made  the  basis  for  purchase,'  because  a  correction  is  thus 
made  for  the  amount  of  moisture  in  the  coal.  It  should  be  noted  that 
this  value  will  in  all  cases  be  lower  than  the  British  thermal  units  in 
the  dry  coal,  which  is  usually  given  in  connection  with  the  coal  analysis. 
The  percentage  of  ash  is  also  specified,  as  it  is  a  factor  in  the  successful 
burning  of  the  coal  on  the  grate  and  as  it  involves  an  expense  for 
removal  from  the  premises. 


COAL   AND   FUEL  OIL  SPECIFICATIONS. 


121 


The  following  are  the  essential  features  of  the  contracts  on  which 
a  Chicago  company  is  said  to  purchase  and  inspect  nearly  1,000,000 
tons  of  coal  for  its  clients  in  Chicago,  Indianapolis,  Minneapolis, 
St.  Louis,  and  other  cities: 

I.  The  company  agrees  to  furnish  and  deliver  to  the  consumer 

at  such  times  and  in  such  quantities  as  ordered  by  the 

consumer  for  consumption  at  said  premises  during  the  term  hereof, 
at  the  consumer's  option,  either  or  all  of  the  kinds  of  coal  described 
below;  said  coals  to  average  the  following  assays: 


Of  size  passing  through  screen  having  circu- 
lar perforations  in  diameter  

....  inches 

....  inches 

.  .  .  .inches 

Of  size  passing  over  a  screen  having  circular 
perforations  in  diameter  
Per  cent  of  moisture  in  coal  as  delivered 

.  .  .  .inches 

.  .  .  .inches 

.  .  .  .inches 

Per  cent  of  ash  in  coal  as  delivered  

British  thermal  units  per  pound  of  dry  coal. 

From  following  county  

Prom  following  State           .           

Coal  of  the  above  respective  descriptions  and  specified  assays  (not 
average  assays)  to  be  hereinafter  known  as  the  contract  grade  of  the 
respective  kinds. 

II.  The  consumer  agrees  to  purchase  from  the  company  all  the  coal 
required  for  consumption  at  said  premises  during  the  term  of  said 
contract,  except  as  set  forth  in  Paragraph  III  below,  and  to  pay  the 
company  for  each  ton  of  2000  Ibs.  avoirdupois  of  coal  delivered  and 
accepted  in  accordance  with  all  the  terms  of  this  contract  at  the  follow- 
ing contract  rate  per  ton  for  coal  of  each  respective  contract  grade, 
at  which  rates  the  company  will  deliver  the  following  respective  numbers 
of  British  thermal  units  for  i  cent,  the  contract  guaranty: 


Kind  of  Coal. 

Contract 
Rate  per 
Ton. 

Contract  Guaranty. 

$.  .. 

equal  to                      net  B  T  U   for  i  cent 

$ 

equal  to                      net  B  T  U   for  i  cent 

$  

equal  to  net  B.T.U.  for  i  cent 

Said  net  British  thermal  units  for  i  cent  being  in  each  case  deter- 
mined as  follows:  Multiply  the  number  of  British  thermal  units  per 
pound  of  dry  coal  by  the  per  cent  of  moisture  (expressed  in  decimals), 


122,  APPENDIX. 

subtract  the  product  so  found  from  the  number  of  British  thermal  units 
per  pound  of  dry  coal,  multiply  the  remainder  by  2000,  and  divide 
this  product  by  the  contract  rate  per  ton  (expressed  in  cents)  plus 
one-half  of  the  ash  percentage  (expressed  as  cents). 

III.  It  is  provided  that  the  consumer  may  purchase  for  consumption 
at  said  premises  coal  other  than  herein  contracted  for,  for  test  purposes, 
it  being  understood  that  the  total  of  such  coal  so  purchased  shall  not 
exceed  5  per  cent  of  the  total  consumption  during  the  term  of  this 
contract. 

IV.  It  is  understood  that  the  company  may  deliver  coal  hereunder 
containing  as  high  as  3  per  cent  more  ash  and  as  high  as  3  per  cent 
more  moisture  and  as  low  as  500  fewer  British  thermal  units  per  pound 
dry  than  specified  above  for  contract  grades. 

V.  Should   any   coal   delivered   hereunder   contain   more   than   the 
per  cent  of  ash  or  moisture  or  fewer  than  the  number  of  British  thermal 
units  per  pound  dry  allowed  under  Paragraph  IV  hereof,  the  con- 
sumer may,  at  its  option,  either  accept  or  reject  same. 

VI.  All  coal  accepted  hereunder  shall  be  paid  for  monthly  at  a  price 
per  ton  determined  by  taking  the  average  of  the  delivered  values 
obtained  from  the  analyses  of  all  the  samples  taken  during  that  month, 
said  delivered  value  in  each  case  being  obtained  as  follows:    Multiply 
the  number  of  British  thermal  units  delivered  per  pound  of  dry  coal 
by  the  per  cent  of  moisture  delivered  (expressed  in  decimals),  subtract 
the  product  so  found  from  the  number  of  British  thermal  units  delivered 
per  pound  of  dry  coal,  multiply  the  remainder  by  2000,  divide  this 
product  by  the  contract  guaranty,  and  from  this  quotient  (expressed 
as  dollars  and  cents)  subtract  one-half  of  the  ash  percentage  delivered 
(expressed  as  cents). 

The  following  are  the  essential  features  of  the  specifications  used 
by  the  Interborough  Rapid  Transit  Company  of  New  York  in  pur- 
chasing about  30,000  tons  of  coal  each  month  for  use  in  its  plants, 
which  are  among  the  largest  in  the  United  States: 

PRELIMINARY  SPECIFICATIONS  FOR  BITUMINOUS  COAL  FOR  THE  INTER- 
BOROUGH  RAPID  TRANSIT  COMPANY. 

Coal  must  be  a  good  steam,  caking,  run-of-mine,  bituminous  coal  free 
from  all  dirt  and  excessive  dust,  a  dry  sample  of  which  will  approximate 
the  company^  standard  in  heat  value  and  analysis  as  follows:  Carbon, 
71;  volatile  matter,  2o;~ash,  9;  B.T.U.,  14,100;  sulphur,  1.50. 


COAL    AND   FUEL  OIL    SPECIFICATIONS.          123 

A  small  quantity  of  coal  will  be  taken  from  each  weighing  hopper 
just  before  the  hopper  is  dumped  while  the  lighter  is  being  unloaded. 
These  quantities  will  be  thrown  into  a  receptacle  provided  for  the 
purpose,  and  when  the  lighter  is  empty  the  contents  of  the  receptacle 
will  be  thoroughly  mixed,  and  a  sample  of  this  mixture  will  be  taken 
for  chemical  analysis.  This  average  sample  of  coal  will  be  labeled  and 
held  for  one  week  after  the  unloading  of  the  lighter.  The  sample  taken 
from  the  mixture  for  test  will  be  analyzed  as  soon  as  possible  after 
being  taken.  No  other  sample  will  be  recognized. 

Tests  of  sample  taken  from  average  sample  will  be  made  by  the 
company's  chemist  under  the  supervision  of  the  superintendent. 
Should  the  contractor  question  the  results  of  the  company's  test  (a 
copy  of  which  will  be  mailed  to  him),  the  company  will,  if  requested 
by  the  contractor  within  three  days  after  copy  of  test  has  been  mailed 
to  him,  forward  sufficient  quantity  of  the  average  sample  taken  from 
each  weighing  hopper  to  any  laboratory  in  the  city  of  New  York  which 
may  be  agreed  upon  by  the  superintendent  and  the  contractor,  and 
have  said  sample  analyzed  by  it,  and  the  results  obtained  from  this 
second  test  will  be  considered  as  final  and  conclusive.  In  case  the 
disputed  values,  as  obtained  in  the  company's  test,  shall  be  found  by 
the  second  test  to  be  2  per  cent  or  less  in  error,  then  the  cost  of  said 
second  test  shall  be  borne  by  the  contractor;  but  if  the  disputed 
values  shall  be  found  to  be  more  than  2  per  cent  in  error,  then  the  cost 
of  said  second  test  shall  be  borne  by  the  company. 

Should  there  be  no  question  raised  by  the  contractor  within  the 
three  days  specified,  as  to  the  values  of  the  first  analysis,  the  average 
sample  of  coal  will  be  destroyed  at  the  end  of  seven  days  from  date  of 
discharge  of  coal  from  lighter.  Should  a  second  test  be  made  of  coal 
taken  from  any  lighter  as  herein  provided,  then  any  penalties  to  be 
made  as  set  forth  in  paragraph  under  "  Penalties"  will  be  based  on 
the  results  as  obtained  from  the  second  test. 

The  price  to  be  paid  by  the  company  per  ton  per  lighter  of  coal  will 
be  based  on  a  table  of  heat  values  for  excess  or  deficiency  of  its  standard, 
but  subject  to  deductions  as  given  in  the  section  under  "Penalized 
coal,"  including  excess  of  ash,  volatile  matter,  sulphur,  or  dust,  or  less 
than  the  minimum  amount  required  to  be  contained  in  any  lighter, 
for  coal  which  shows  results  less  than  the  company's  standard. 

Premiums  or  deductions  are  based  on  a  rate  of  i  cent  per  ton  for  a 
variation  of  50  B.T.U.  per  pound  of  coal,  as  indicated  in  a  table  a 
few  items  of  which  are  given  below: 


124  APPENDIX. 

Table  for  B.T.U.  Values. 

For  coal  in  any  lighter  which  is  found  by  test  to  contain,  per  pound 
of  dry  coal,  from 

15,501  and  above 28  cents  per  ton  above  standard 

15,101  to  15,150,  both  inclusive 20  cents  per  ton  above  standard 

14,601  to  14,650,  both  inclusive 10  cents  per  ton  above  standard 

14,101  to  14,150,  both  inclusive Standard 

13,601  to  13,650,  both  inclusive 10  cents  per  ton  below  standard 

13,101  to  13,150,  both  inclusive 20  cents  per  ton  below  standard 

12,101  to  12,150,  both  inclusive 40  cents  per  ton  below  standard 

No  lighter  of  coal  will  be  accepted  which,  by  trial,  in  the  judgment 
of  the  superintendent,  contains  an  excessive  amount  of  dry  coal  dust. 
The  decision  of  the  superintendent  will  be  final  in  this  respect.  Coal 
taken  from  such  lighter  for  trial  will  be  subject  to  the  special  deduction 
set  forth  under  "Penalized  coal,"  but  paid  for  in  all  other  respects  as 
herein  provided. 

Coal  which  is  shown  by  analysis  to  contain  less  than  20  per  cent  of 
volatile  matter,  9  per  cent  of  ash,  or  1.50  per  cent  of  sulphur,  will  be 
accepted,  without  a  deduction  from  the  bidder's  price,  plus  or  minus 
an  amount  for  excess  or  deficiency  of  British  thermal  unit  value,  as 
herein  provided.  Where  the  analysis  gives  amounts  for  any  or  all 
elements  in  excess  of  these  quantites,  deductions  will  be  made  from 
the  bidder's  price  in  accordance  with  the  tables  of  values  of  volatile 
matter,  ash,  and  sulphur  below  given,  plus  or  minus  the  amount  for 
excess  or  deficiency  of  the  standard  British  thermal  unit  value,  in 
addition  to  any  other  deductions  which  may  be  made  as  herein  pro- 
vided. 

Table  of  Deductions  for  Volatile  Matter. 

For  coal  in  any  lighter  which  is  found  by  test  to  contain,  per  pound  of 
dry  coal 

Over  20  per  cent  and  less  than  21  per  cent 2  cents  per  ton 

********* 

Over  22.5  per  cent  and  less  than  23  per  cent ....   12  cents  per  ton 
********* 

24  per  cent  and  over 18  cents  per  ton 

This  table  is  made  for  the  difference  of  each  one-half  of  i  per  cent 
and  the  deductions  are  at  the  rate  of  4  cents  for  each  i  per  cent  of 
volatile  matter. 


COAL   AND  FUEL  OIL  SPECIFICATIONS.  125 

Table  of  Deductions  for  Ash. 

For  coal  in  anylighter  which  is  found  by  test  to  contain,  per  pound  of 
dry  coal 

Over  9  per  cent  and  less  than  9.5  per  cent 2  cents  per  ton 

********* 

Over  11.5  per  cent  and  less  than  12 12  cents  per  ton 

********* 

13.5  per  cent  and  over 23  cents  per  ton 

This  table  is  made  for  each  difference  of  one-half  of  i  per  cent  and 
at  the  rate  of  4  cents  for  each  i  per  cent  increase  in  the  ash. 

Table  of  Deductions  for  Sulphur. 

For  coal  in  any  lighter  which  is  found  by  test  to  contain,  per   pound  of 
dry  coal 

Over  1.50  per  cent  and  less  than  1.75  per  cent  .  .     6  cents  per  ton 
********* 

Over  2  per  cent  and  less  than  2.25  per  cent 10  cents  per  ton 

********* 

2.50  and  over 20  cents  per  ton 

This  table  is  made  out  for  each  difference  of  one-fourth  of  i  per  cent 
and  at  a  diminishing  rate. 

Should  any  lighter  of  coal  delivered  at  the  company's  docks  contain 
less  than  700  tons,  a  deduction  of  7  cents  per  ton  will  be  made  from 
the  price  as  determined  by  the  British  thermal  unit  value  and  analysis, 
in  addition  to  any  other  penalty  provided  for  herein.  Should  any 
lighter  of  coal  delivered  at  the  company's  docks  be  rejected  by  the  super- 
intendent on  account  of  excessive  amount  of  coal  dust,  then  a  reduction 
of  25  cents  per  ton  will  be  made  from  the  price  as  determined  by  the 
British  thermal  unit  value  and  analysis,  for  the  coal  taken  from  said 
lighter,  in  addition  to  any  other  penalty  which  may  be  made  as  herein 
provided.  Should  any  lighter  of  coal  be  delivered  in  other  than  self- 
trimming  lighters  as  herein  provided,  a  deduction  of  7  cents  per  ton 
will  be  made  from  the  price  as  determined  by  the  British  thermal  unit 
value  and  analysis,  exclusive  of  any  other  penalty  which  may  be  made 
as  herein  provided. 

The  contractor's  bill  of  lading  will  be  checked  by  the  company's 
scales.  Should  there  be  a  deficiency  of  i  per  cent  or  more  between 


126  APPENDIX. 

the  bill  of  lading  and  the  company's  weights,  then  the  company's 
weights  will  be  taken  as  correct. 

When  the  contractor  has  been  notified  by  the  company  to  deliver 
coal  under  this  contract,  a  further  notice  may  be  given  requiring  the 
contractor  to  make  delivery  of  the  coal  so  ordered  within  twelve  hours 
after  the  receipt  of  said  second  notice.  Should  the  contractor,  for  any 
reason,  fail  to  deliver  the  coal  so  ordered  within  twelve  hours  after 
the  receipt  of  said  second  notice  and  in  accordance  with  the  require- 
ments therein  as  to  place  of  delivery,  the  company  shall  be  at  liberty 
to  buy  coal  in  the  open  market,  and  the  contractor  will  make  good 
to  the  company  any  difference  there  may  be  between  the  price  paid 
by  the  company  for  said  coal  in  open  market  and  the  price  the  com- 
pany would  have  paid  to  the  contractor  had  the  coal  been  delivered 
by  it  in  accordance  with  the  requirements  of  said  notices  from  the 
company,  or  said  difference  may  be  deducted  from  any  money  then 
due  or  thereafter  to  become  due  to  the  contractor  under  the  contract 
to  be  entered  into. 


FUEL  OIL  SPECIFICATIONS. 

The  Specifications  of  the  U.  S.  Government  are  as  follows*: 

GENERAL  SPECIFICATIONS. 

(1)  In  determining  the  award  of  a  contract,  consideration  will  be 
given  to  the  quality  of  the  fuel  offered  by  the  bidders,  as  well  as  the 
price,  and  should  it  appear  to  be  to  the  best  interest  of  the  Govern- 
ment to  award  a  contract  at  a  higher  price  than  that  named  in  the 
lowest  bid  or  bids  received,  the  contract  will  be  so  awarded. 

(2)  Fuel  oil  should  be  either  a  natural  homogeneous  oil  or  a  homo- 
geneous residue  from  a  natural  oil ;  if  the  latter,  all  constituents  having 
a  low  flash-point  should  have  been  removed  by  distillation;    it  should 
not  be  composed  of  a  light  oil  and  a  heavy  residue  mixed  in  such  pro- 
portions as  to  give  the  density  desired. 

(3)  It  should  not  have  been  distilled  at  a  temperature  high  enough 
to  burn  it,  nor  at  a  temperature  so  high  that  flecks  of  carbonaceous 
matter  began  to  separate. 

*  J.  C.  Allen,  J.  Ind.  and  Bag.  Chem.,  3,  730  (1911). 


COAL   AND   FUEL  OIL  SPECIFICATIONS.         127 

(4)  It  should  not  flash  below  60°  C.  (140°  F.)  in  a  closed  Abel- 
Pensky  or  Pensky-Martens  tester. 

(5)  Its  specific  gravity  should  range  from  0.85  to  0.96  at  15°  C. 
(59°  F.) ;    the  oil  should  be  rejected  if  its  specific  gravity  is  above  0.97 
at  that  temperature. 

(6)  It  should  be  mobile,  free  from  solid  or  semi-solid  bodies,  and 
should  flow  readily,  at  ordinary  atmospheric  temperatures  and  under 
a  head  of  i  foot  of  oil,  through  a  4-inch  pipe  10  feet  in  length. 

(7)  It  should  not  congeal  nor  become  too  sluggish  to  flow  at  o°  C. 
(32°  F.). 

(8)  It  should  have  a  calorific  value  of  not  less  than  10,000  calories 
per  gram  *  (18,000  B.T.U.  per  pound),  10,250  calories  to  be  the  standard. 
A  bonus  is  to  be  paid  or  a  penalty  deducted  according  to  thejnethod 
stated  under  Section  21,  as  the  fuel  oil  delivered  is  above  or  below 
this  standard,  f 

(9)  It  should  be  rejected  if  it  contains  more  than  2  per  cent  water. 

(10)  It  should  be  rejected  if  it  contains  more  than  i  per  cent  sulphur, 
(n)  It  should  not  contain  more  than  a  trace  of  sand,  clay,  or  dirt. 

(12)  Each   bidder  must  submit  an   accurate   statement    regarding 
the  fuel  oil  he  proposes  to  furnish.    This  statement  should  show: 

(a)  The  commercial  name  of  the  oil. 

(&)  The  name  or  designation  of  the  field  from  which  the  oil  is  obtained. 

(c)  Whether  the  oil  is  a  crude  oil,  a  refinery  residue,  or  a  distillate. 

(d)  The  name  and  location  of  the  refinery ,[ii  the  oil  has  been  refined 
at  all. 

(13)  The   fuel   oil  is  to  be  delivered  f.o.b.  cars  or  vessel,  according 
to  the  manner  of  shipment,  at  such  places,  at  such  times,  and  in  such 
quantities  as  may  be  required,  during  the  fiscal  year  ending 

(14)  Should  the  contractor,  for  any  reason,  fail  to  comply  with  a 
written  order  to  make  delivery,  the  Government  is  to  be  at  liberty  to 
buy  oil  in  the  open  market,  and  charge  against  the  contractor  any  excess 
of  price,  above  the  contract  price,  of  the  fuel  oil  so  purchased. 

*  Calories X i. 8  =  B.T.U.  per  pound. 

t  It  is  important  that  the  standard  fixed  should  not  be  higher  than  can  be 
maintained  under  the  terms  of  the  contract.  In  the  absence  of  information 
as  to  the  heating  value  of  the  oil,  the  Bureau  of  Mines  will  analyze  samples 
taken  from  the  deliveries  to  establish  the  standard  heating  value,  expressed 
in  calories  or  B.T.U.  It  will  be  to  the  best  interests  of  the  contractor  to  specify 
a  fair  standard  for  the  fuel  oil  he  offers,  since  failure  to  maintain  that  standard 
will  cause  deduction  from  the  contract  price  and  possibly  the  cancellation 
of  the  contract,  while  deliveries  of  higher  quality  than  the  standard  will  result 
in  the  contractor  receiving  premiums. 


128  APPENDIX. 


SAMPLING. 

(15)  Deliveries  of  fuel  oil  will  be  sampled  by  a  representative  of  the 
Government.    Whenever  such  action  is  practicable,   the  oil  will  be 
sampled  as  it  is  being  delivered.     The  final  sample  will  be  made  from 
samples  taken  from  as  large  a  proportion  of  the  delivery  as  practicable, 
in  order  that  the  final  sample  may  truly  represent  the  delivery. 

(16)  The  final  sample  will  be  sealed  and  forwarded  to  the  Federal 
Bureau  of  Mines,  Pittsburgh,  Pa.,  for  analysis. 

(17)  If  the  contractor  so  desires,  permission  will  be  given  him,  or 
his  representative,  to  witness  the  sampling  of  the  delivery  and  the 
preparation  of  the  final  sample. 

(18)  The  final  sample  will  be  analyzed  and  tested  immediately  after 
its  receipt  in  Pittsburgh. 

CAUSES  FOR  REJECTION.    * 

(19)  A  contract  entered  into  under  the  terms  of  these  specifications 
shall  not  be  binding  if,  as  the  result  of  a  practical  service  test  of  reason- 
able duration,  the  fuel  oil  fails  to  give  satisfactory  results. 

(20)  It  is  understood  that  the  fuel  oil  delivered  during  the  terms  of 
the  contract  shall  be  of  the  quality  specified.     The  frequent  or  con- 
tinued failure  of  the  contractor  to'deliver  oil  of  the  specified  quality 
will  be  considered  sufficient  cause  for  the  cancellation  of  the  contract. 

PRICE  AND  PAYMENT. 

(21)  Payment  for  deliveries  will  be  made  on  the  basis  of  the  price 
named  in  the  proposal  for  the  fuel  oil  corrected  for  variations  in  heat- 
ing value,*  as  shown  by  analysis,  above  cr  below  the  standard  fixed 
by  the  contractor.     This  correction  is  a  pro  rata  one  and  the  price  is 
to  be  determined  by  the  following  formulae: 

Delivered  calories  per  gram  (or  B.T.U.  per  lb.)Xcontract  price 
Standard  calories  per  gram  (or  B.T.U.  per  Ib.) 

=  price  to  be  paid. 

*  The  value  of  an  oil  as  fuel  is  in  proportion  to  the  total  combustible  matter 
it  contains  as  shown  by  its  heating  value.  This  value  may  be  expressed  in 
small  calories  per  gram  of  B.T.U.  per  pound.  Sulphur,  moisture,  and  earthy 
matter  lower  the  heating  value  of  an  oil  and  decrease  the  furnace  capacity; 
they  also  may  have  a  deleterious  effect  on  boiler  and  furnace,  and  may  impair 
the  operation  of  burners. 


COAL   AND    FUEL  OIL   SPECIFICATIONS.          129 

Water  that  accumulates  in  the  receiving  tank  will  be  drawn  off  and 
measured  periodically.  Proper  deduction  will  be  made  by  subtracting 
the  weight  of  the  water  from  the  weight  of  the  oil  deliveries. 

DETERMINATION  OF  WEIGHT  FROM  VOLUME. 

The  specifications  given  on  the  preceding  pages  provide  for  the 
purchase  of  fuel  oil  by  weight.  As  such  oil  is  frequently  delivered  by 
volume,  it  is  important  to  note  the  temperature  of  a  delivery  and  to 
allow  for  the  expansion  due  to  this  temperature  when  computing  the 
weight  of  the  delivery  from  the  volume.  From  the  volume  of  the  oil 
at  the  temperature  of  delivery,  the  volume  at  standard  temperature 
(15°  C.)  should  be  computed  in  the  manner  given  below. 

The  coefficient  of  expansion  of  ordinary  fuel  oil  residues  of  asphaltic 
base  is  approximately  0.0006  per  i°  C. 

Hence  if  the  temperature  (N°  C.)  of  the  delivery  is  above  15°  C., 
then  (N°  C.  — 15°  C.)  X 0.0006  =  correction. 

This  correction  is  to  be  added  to  the  specific  gravity  at  N°  C.  to 
give  the  standard  specific  gravity,  that  at  15°  C. 

If  the  temperature  (N°  C.)  of  the  oil  delivered  is  below  15°  C.,  the 
correction  ((15°  C.—  N°  C.)  X 0.0006)  is  to  be  subtracted  from  the 
specific  gravity  at  15°  C. 

Since  a  gallon  of  water  at  a  temperature  of  15°  C.  weighs  8.3316  Ibs., 
the  weight  in  pounds  of  a  gallon  of  oil  at  15°  C.  is  8.3316  times  the  specific 
gravity  of  the  oil  at  that  temperature. 

Similarly,  since  a  cubic  foot  of  water  at  15°  C.  weighs  62.3425  Ibs., 
the  weight  in  pounds  of  a  cubic  foot  of  oil  at  15°  C.  is  62.3425  times  its 
specific  gravity  at  that  temperature. 

REPORTING  ANALYSES  OF  FUEL  OIL. 

The  following  form  is  used  by  the  Bureau  of  Mines  in  reporting  the 
results  of  an  analysis  of  a  sample  of  fuel  oil : 

DEPARTMENT   OF  THE   INTERIOR. 

BUREAU  OF  MINES. 

WASHINGTON,  D.  C.,  IQI — . 

SIR: 

In  reference   to   the sample  of   fuel   petroleum  represent- 

(Quantity.) 

ing of  petroleum  delivered  at  a  temperature  of          °  C  by 

(Quantity.) 

the as  a product,  from  the 

(Company  delivering.)    (Crude,  residue,  or  distillate.)  (Lease.) 


130  APPENDIX. 

,   , '. ,  to  the  , 

(Field  or  district.)         (County.)  (State.)  (Department  receiving.) 

at on ,  I    have    the    honor    to    report    as 

(City.)  (Date  of  delivery.) 

follows : 

Specific  gravity  at  15°  C 

(Baume  at  59°  F.) 

Calorie  per  gram 

(B.T.U.  per  pound) 

Water,  per  cent 

Sulphur,  per  cent 

Earthy  matter,  sand,  etc.,  per  cent 

Flash-point,  °  C.  (Abel-Pensky,  or  Pensky-Mar- 

tens,  closed  tester) 

Burning  point,  °  C.  (same  tester,  opened) 

Remarks: 


The  above  information  is  for  the  use  of  the  Government  and  the  dealer  or 
operator  furnishing  the  oil.  It  is  to  be  considered  confidential  until  it  is  pub- 
lished by  the  United  States  Government. 

Respectfully, 

Chief  Clerk. 
Certified: 

Petroleum  Chemist. 
SAMPLING   PETROLEUM   OR   FUEL  OIL. 

GENERAL   STATEMENT. 

The  accuracy  of  the  sampling  and,  in  turn,  the  value  of  the  analysis 
must  necessarily  depend  on  the  integrity,  alertness,  and  ability  of  the 
person  who  does  the  sampling.  No  matter  how  honest  the  sampler 
may  be,  if  he  lacks  alertness  and  sampling  ability,  he  may  easily  make 
errors  that  will  vitiate  all  subsequent  work  and  render  the  results  of 
tests  and  analyses  utterly  misleading.  A  sampler  must  be  always  on 
the  alert  for  sand,  water,  and  foreign  matter.  He  should  note  any 
circumstances  that  appear  suspicious,  and  should  submit  a  critical 
report  on  them,  together  with  samples  of  the  questioned  oil. 


COAL  AND   FUEL   OIL  SPECIFICATIONS.  131 

SAMPLING  WAGON  DELIVERIES. 

SAMPLING  WITH  A  DIPPER. 

Immediately  after  the  oil  begins  to  flow  from  the  wagon  to  the 
receiving  tank,  a  small  dipper  holding  any  definite  quantity,  say,  0.5 
liter  (about  i  pint),  is  filled  from  the  stream  of  oil.  Similar  samples 
are  taken  at  equal  intervals  of  time  from  the  beginning  to  the  end  of 
the  flow — a  dozen  or  more  dipperfuls  in  all.  These  samples  are  poured 
into  a  clean  drum  and  well  shaken.  If  the  oil  is  heavy,  the  dipperfuls 
of  oil  may  be  poured  into  a  clean  pail  and  thoroughly  stirred.  FOL  a 
complete  analysis  the  final  sample  should  contain  at  least  4  liters  (about 
i  gallon).  This  sample  should  be  poured  into  a  clean  can,  soldered 
tight  and  forwarded  to  the  laboratory. 

It  is  important  that  the  dipper  be  filled  with  oil  at  uniform  intervals 
of  time  and  that  the  dipper  be  always  filled  to  the  same  level.  The 
total  quantity  of  oil  taken  should  represent  a  definite  quantity  of  oil 
delivered  and  the  relation  of  the  sample  to  the  delivery  should  be 
always  be  stated,  for  instance:  "i  gallon  sample  representing  i  wagon- 
load  of  20  barrels." 

CONTINUOUS  SAMPLING. 

Instead  of  taking  samples  with  a  dipper,  it  may  be  more  convenient 
to  take  a  continuous  sample.  This  may  be  taken  by  allowing  the 
oil  to  flow  at  a  constant  and  uninterrupted  rate  from  a  £-inch  cock  on 
the  under  side  of  the  delivery  pipe  during  the  entire  time  of  discharge. 
The  continuous  sample  should  be  thoroughly  mixed  in  a  clean  drum 
or  pail,  and  at  least  4  liters  (about  i  gallon)  of  it  forwarded  for  analysis. 
A  careful  examination  should  be  made  for  water,  and  if  the  first  dipperful 
shows  water  this  dipperful  should  be  thrown  into  the  receiving  tank 
and  not  mixed  with  the  sample  for  analysis. 

MIXED  SAMPLES. 

If  the  oil  delivered  during  any  definite  period  of  time,  say  one  month, 
be  from  the  same  source  and  of  uniform  quality  (but  only  in  case  it  is 
of  uniform  quality),  it  may  suffice  to  pour  definite  proportional  quanti- 
ties of  the  dipper  and  the  continuous  samples  taken  during  this  period 
into  a  tinned  can  or  drum  having  a  tight  screw  cap  or  bung.  An  iron 
drum  should  not  be  used,  since  even  a  clean  iron  surface  will  absorb 
sulphur  by  long  contact  with  a  sulphur-containing  oil,  and  this  sulphur 
will  be  lost  to  the  analyst.  At  the  end  of  the  month  a  number  of  round, 


132  APPENDIX. 

clean  stones  should  be  put  into  the  drum  and  the  drum  should  be  rolled 
to  insure  intimate  mixing.  Then  4  liters  (about  i  gallon)  of  the  gross 
sample  should  be  taken  for  analysis.  The  drum  should  be  drained, 
rinsed  clean  with  gasoline,  dried,  and  made  ready  for  a  second  sampling. 
The  all-important  point  is  that  the  gross  sample,  whatever  the 
manner  of  sampling,  shall  be  made  up  of  equivalent  portions  of  oil 
taken  at  regular  intervals  of  time,  so  that  the  sample  finally  forwarded 
for  analysis  will  truly  represent  the  entire  shipment. 

SAMPLING  A  LARGE  TANK  OR  RESERVOIR. 

Water  or  earthy  matter  settles  on  standing.  Hence,  before  a  large 
stationary  tank  or  reservoir  is  sampled  the  character  of  the  contents 
at  the  bottom  should  be  ascertained  by  dredging  with  a  long-handled 
dipper,  and  the  content  of  the  dipper  should  be  examined  critically. 
If  a  considerable  quantity  of  sediment  is  brought  up,  it  should  be  cause 
for  rejecting  the  oil. 

The  sampling  of  a  large  stationary  tank  or  reservoir  of  oil,  par- 
ticularly if  the  oil  has  stood  so  long  that  it  has  begun  to  stratify,  or 
form  layers  of  different  density,  may  be  done  as  follows: 

The  sampler  should  procure  an  ordinary  iron  pipe,  or  preferably  a 
tinned  tube,  i  inch  in  diameter  and  long  enough  to  reach  from  above 
the  manhole,  where  he  can  grasp  it,  to  the  bottom  of  the  tank.  The 
lower  end  of  the  pipe  should  be  reamed  out  with  a  round  file.  A  conical 
plug  of  cork,  wood,  or  other  suitable  material  should  be  fitted  to  this 
end,  and  a  strong,  stiff  wire,  such  as  the  ordinary  telegraph  wire,  run 
through  this  plug  and  up  through  the  pipe  to  a  point  where  it  can  be 
grasped  firmly  by  the  sampler.  A  pull  on  the  wire  will  close  the 
bottom  of  the  pipe,  and  a  rap  against  the  bottom  of  the  tank  will  drive 
the  plug  home  and  make  an  oil-tight  seal  or  valve. 

To  operate  this  sampling  device,  the  sampler  should  remove  the 
plug,  allow  it  to  drop  some  three  inches  below  the  bottom  of  the  pipe, 
and  let  it  hang  there  by  the  wire  extending  above  the  pipe.  Then 
holding  the  pipe,  open  at  top  and  bottom,  in  a  vertical  position,  the 
sampler  should  allow  it  to  sink  slowly  through  the  oil  to  the  bottom 
of  the  tank.  He  should  do  this  slowly  and  with  care,  so  that  the  pipe 
will  penetrate  the  oil  without  agitating  it  and  will  thus  cut  a  repre- 
sentative core  of  oil  from  the  surface  to  the  bottom.  When  the  pipe 
touches  the  bottom,  the  sampler  should  draw  up  the  slack  of  the  wire 
and  pull  the  plug  into  place;  then  he  should  strike  the  plug  smartly 
against  the  bottom  of  the  .tank,  thereby  driving  it  home  and  sealing 


COAL    AND   FUEL   OIL    SPECIFICATION'S.         133 

the  pipe.  He  can  then  withdraw  the  pipe  and  pour  the  oil  into  the 
sampling  can.  If  it  seems  desirable^he  should  "core  "  or  "sample" 
a  reservoir  at  regularly  spaced  points,  unite  these  samples,  mix  them 
thoroughly,  and  take  4  liters  (about  i  gallon)  of  the  gross  sample  for 
analysis. 

Instead  of  a  pipe  sampler,  a  bottle  holding  half  a  liter  (about  i  pint) 
may  be  used.  It  should  be  securely  fastened  to  a  long  pole  and  have 
a  loosely-fitted  stopper  tied  to  a  strong  cord.  The  bottle,  corked  and 
empty,  is  immersed  to  any  desired  point  within  the  mass  of  oil,  and  the 
stopper  is  pulled  out.  The  bottleful  of  oil  is  poured  into  a  suitable 
receiving  vessel,  and  the  bottle  thoroughly  drained  is  made  ready  for 
a  second  filling.  Bottlefuls  of  oil  taken  in  this  way  from  points  sym- 
metrically placed  throughout  the  mass  of  oil,  will,  if  properly  mixed, 
provide  an  excellent  gross  sample  from  which  to  take  the  4-liter  (i  gallon) 
sample  for  analysis. 

SAMPLING  A  SINGLE  DRUM. 

A  single  drum  may  be  sampled  with  a  glass  tube.  This  tube,  open 
at  both  ends,  should  be  grasped  at  the  top,  held  vertically,  inserted  in 
the  drum  without  agitating  the  oil,  and  allowed  to  cut  its  way  slowly 
to  the  bottom  of  the  drum.  The  upper  end  should  then  be  closed  with 
the  thumb  or  forefinger  of  the  hand  holding  it,  the  tube  withdrawn, 
and  the  oil  on  the  outside  wiped  off  with  the  fingers  of  the  other  hand. 
The  sample  in  the  tube  can  then  be  transferred  to  a  small  can,  and 
forwarded  for  analysis. 

FORWARDING  SAMPLES. 

The  sample  should  be  forwarded  in  a  glass  bottle  or  carboy  or  in  a 
tin  can,  preferably  in  the  latter,  because  less  liable  to  breakage.  If  a 
tin  can  is  used  the  cap  should  be  soldered  tight.  The  can  should  not 
be  filled  completely;  about  an  eighth  of  an  inch  of  space  should  be 
left  to  allow  for  possible  expansion  of  the  oil. 

The  can  should  be  sealed  as  soon  as  it  is  filled  to  avoid  loss  by  vola- 
tilization of  the  lighter  constituents  of  the  sample.  After  the  can  has 
been  filled  and  tightly  soldered,  it  should  be  wiped  clean  and  carefully 
examined  for  pinholes  or  small  leaks.  All  leaks  should  be  soldered 
before  the  can  is  packed  for  shipment. 

The  bottle  or  can  should  be  carefully  labeled.  The  following  form 
of  label,*  used  by  the  Bureau  of  Mines,  should  be  placed  on  samples 
shipped  to  the  bureau: 

*  These  labels  will  be  furnished  on  request. 


134  APPENDIX. 

DEPARTMENT  OF  THE  INTERIOR. 

BUREAU  OF  MINES. 

Information  to  Accompany  Each  Sample  of  Fuel  Petroleum  Submitted 
for  Analysis. 

Sample  number Sampled  by 

Oil  delivered  to , 

(Department  receiving.) 

Place  of  delivery 

(City.)  (State.) 

Quantity  of  oil  delivered 

Date  of  delivery 

Temperature  of  oil  as  delivered °  C 

Name  of  contractor 

Nature  of  oil 

(Crude,  residue,  or  distillate.) 

If  refined  to  any  degree,  state  name  and  location  of  refinery 

Source  of  oil 

(Lease.)  (Field  or  district.)          (County.)  (State.) 

Remarks.  . 


Date  of  forwarding  sample 

Forwarded  by via 

(Express  or  fast  freight.)  (Transportation  line.) 


Date  of  receipt  of  sample  by  Bureau  of  Mines 

Condition  of  sample  when  received  by  Bureau  of  Mines . 


The  label  should  be  carefully  written  with  a  hard  lead  pencil  on  a 
strong  mailing  tag,  and  this  tag  should  be  securely  tied  to  the  can. 
The  lead  pencil  should  be  pressed  firmly  against  the  tag  so  as  to  indent 
its  surface.  An  inscription  thus  written  is  legible  even  after  the  paper 
has  been  wet  with  oil.  Gummed  labels  should  not  be  used;  they  are 
easily  detached  if  slightly  moistened,  and  may  be  lost.  A  duplicate 
copy  of  the  record  on  the  label  should  be  mailed  to  the  engineer  in  charge, 
Bureau  of  Mines,  Pittsburgh,  Pa. 


COAL  AND    FUEL    OIL    SPECIFICATIONS.         135 


SAMPLING  GAS  FROM  A  WELL. 

Since  the  gas  associated  with  oil  is  an  ideal  fuel  and  illuminant,  and 
the  literature  dealing  with  the  composition  of  natural  gas  is  scanty, 
a  description  of  the  method  of  sampling  such  gas  for  analysis  is  here 
given. 

For  taking  a  sample  of  gas  under  pressure  from  an  oil  well  a  cloth 
funnel  should  be  made  by  folding  and  sewing  any  strong,  closely-woven 
cloth  into  the  form  of  a  cornucopia.  The  larger  end  of  this  funnel 
should  be  large  enough  to  encompass  the  gas  pipe  from  which  the 
sample  is  to  be  taken.  The  smaller  end,  or  apex,  of  the  funnel  should 
should  be  securely  tied  about  one  end  of  a  flexible  rubber  tube  i  or  2  feet 
long  and  one-fourth  to  one-half  inch  in  diameter.  If  there  is  a  gas  jet 
at  the  well,  one  end  of  the  rubber  tube  may  be  attached  directly  to  the 
jet. 

A  gas-sampling  bottle  should  be  procured,  if  practicable,  from  the 
Bureau  of  Mines,  Pittsburgh,  Pa.  If  such  a  bottle  is  not  at  hand,  a 
i-  or  2-liter  (i-  or  2-quart)  bottle  with  a  well-ground,  tight-fitting  glass 
stopper  may  be  used.  The  bottle  should  be  thoroughly  cleansed  and 
dried.  A  large  perfume  bottle  or  an  acid  bottle,  such  as  may  be  obtained 
from  a  drug  store,  will  usually  answer.  A  glass  stopper  is  essential, 
for  a  cork  or  rubber  stopper  may  leak  even  though  it  appears  to  be 
hermetically  sealed  with  wax;  moreover,  a  cork  or  rubber  stopper 
may  contaminate  the  gas. 

To  collect  a  sample,  the  funnel  should  be  tied  firmly  about  the  end 
of  the  gas  pipe.  The  funnel  and  the  rubber  tube  should  then  be  thor- 
oughly flushed  with  the  gas  to  rid  them  of  air.  The  free  end  of  the  tube 
should  go  to  the  bottom  of  the  sample  bottle.  The  bottle  should  be 
fastened  bottom  up  and  the  gas  allowed  to  blow  strongly  into  it  for  at 
least  a  quarter  of  an  hour  to  insure  complete  expulsion  of  air.  If  the 
gas  pressure  is  low,  the  gas  should  be  allowed  to  blow  longer,  or  until 
it  is  certain  that  all  air  has  been  expelled  from  the  bottle.  Meanwhile 
the  stopper  of  the  bottle  should  have  been  well  greased  with  vaseline. 

While  the  gas  is  still  blowing  through  the  tube  the  tube  should  be 
slowly  withdrawn.  The  stopper  should  be  put  in  just  as  soon  as  the 
tube  is  withdrawn  and  should  be  turned  firmly  into  place.  Then  the 
bottle  should  be  turned  up  and  a  spoonful  of  melted  paraffin  poured 
over  the  stopper.  The  stopper  should  be  secured  with  elastic  band. 

A  strong  tag  should  be  tied  to  the  bottle  by  a  stout  cord.  This  tag 
should  be  labeled  as  follows: 


136  APPENDIX. 

Gas  Sample. 


Sampled  by . 
Date.. 


Well Lease 

Number.  .    _, 

Section Township Range 

District County State 

Remarks . .  


The  bottle  should  be  packed  securely  in  a  box  and  forwarded  to  the 
Bureau  of  Mines,  Pittsburgh,  Pa.  A  duplicate  copy  of  the  label 
should  be  sent  to  the  same  address. 


INDEX. 


PAGE 

Acetylene,  calorific  power  of in 

Acid,  hydrochloric,  reagent 51 

Air-pumps,  Bunsen's 8 

,  Richards' 8 

,  steam 9 

Alcohol,  denatured,  calorific  power  of in 

,  ethyl,  calorific  power  of in 

,  methyl,  calorific  power  of m 

Anthracite  coal,  analysis  of 63 

Aqueous  vapor,  table  of 109 

,  specific  heat 30 

Aspirator 9 

,  Muencke's 56 

Benzophenon,  boiling-point 26 

Berthier's  method  of  determining  calorific  power  of  coal 95 

Bituminous  coal,  analysis  of 62 

,  varieties 61 

Blast-furnace  gas,  analysis  of 0 . .  68 

Boiling-point  of  various  substances 26 

Brown  coal 61 

,  analysis  of 61 

,  calorific  power  of 112 

Bunte's  gas  apparatus 16 

method  for  determining  quantity  of  heat  passing  up  chim- 

ney 32,33 

Calculations „ 28 

Calorimeters  of  Barrua 81 

Fischer  . 81 

Hempel 82 

Mahler 82 

parr- 93 

Thompson,  L. 81 

Thomson,  W 81 

Carbon  dioxide,  determination  of 13,  18,  21,  40 

,  specific  heat ^o 

137 


138  INDEX. 

PAGE 

Carbonic  oxide,  determination  of 14,  19,  22,  40 

,  loss  due  to  formation  of 34 

,  specific  heat 30 

Charcoal,  analysis  of 64 

,  preparation 63 

Coal,  air  required  for  combustion 63 

,  calorific  power 63 

,  formation  of 60 

,  method  of  analysis 70 

specifications 115 

Coal-gas,  analysis  of 69 

,  calorific  power 69 

,  manufacture  of 69 

Coke,  analysis  of 64 

,  calorific  power  of 112 

,  determination  of 69 

,  preparation 64 

Coke-oven  gas,  calorific  power 70 

Coke-ovens 64 

Cooling  correction  in  calorim'etry 92 

Course  in  gas  analysis : 68 

Cuprous  chloride  acid,  reagent 51 

t  ammoniacal,  reagent 52 

Elliott's  gas  apparatus 20 

Formulae,  Bunte's,  for  calorific  power  of  coal 97 

,  Dulong's,  for  calorific  power  of  coal 97 

,  for  heat  of  combustion  with  Mahler  bomb 91 

,  Goutal's,  for  calorific  power  of  coal 98 

,  Lunge's,  for  heat  passing  up  chimney 34 

,  Mahler's,  for  calorific  power  of  coal 97 

,  Noyes',  for  calculation  of  heat  lost 34 

,  Ratio  of  air  used  to  that  theoretically  necessary 32 

Fuel,  determination  of  calorific  power 81,  99 

,  loss  due  to  unconsumed 34 

Fuel  oil,  specifications 126 

Fuels,  method  of  analysis  of:  ash 78 

carbon 74 

coke  and  volatile  matter 73 

hydrogen 74 

moisture 73 


INDEX.  139 

PAGB 

Fuels,  method  of  analysis  of:  nitrogen 78 

oxygen 78 

sulphur 78 

Fuming  sulphuric  acid,  reagent 51 

Gas-balance  of  Custodis 24 

calorimeter,  Junkers' 99 

composimeter  of  Uehling 24 

Gas,  determination  of  calorific  power  by  calculation 103 

,  ignition  temperatures  of no 

laboratory,  arrangement  of 55 

Gasolene,  calorific  power  of in 

Generator  gas,  see  Producer-gas. 

Hempel's  gas  apparatus 36,  47 

Hydrocarbons,  determination  of 14,  23,  40 

Hydrogen,  determination  of 42,  46 

,  reagent 53 

Ignition  temperatures  of  gases no 

" Illuminants,"  calorific  power  of in 

determination  of 41 

Illuminating-gas,  Boston,  analysis  of 104 

,  calorific  power  (calculated) 106 

,  manufacture 70 

,  method  of  analysis  of 40 

Iron  tubes,  action  of  uncooled  gases  upon 2 

Junkers'  gas  calorimeter 99 

Kerosene,  calorific  power  of in 

Laboratory,  arrangement  of 55 

Lead,  quantity  reduced,  a  measure  of  the  calorific  power 95 

Lignite 61 

Mahler  bomb 82 

Melting-point  boxes 27 

Melting-point  of  various  substances 1 13 

Mercury,  reagent 53 

Methane,  determination  of 42,  46 

Moisture  in  coal,  determination  of 73 


140  INDEX. 

PAGE 

Naphthalene,  boiling-point 26 

,  calorific  power 90 

Natural  gas,  analysis  of 68 

,  calorific  power 70 

Nitrogen,  determination  of,  in  coal 78 

,  in  gases 14,  48 

,  specific  heat 30 

Orsat's  gas  apparatus , n 

Otto-Hoffman  coke-ovens 64 

Oxygen,  determination  of,  in  air 40,  41 

,  in  coal 78 

,  in  gases 14,  19,  22,  42 

,  specific  heat 30 

Palladous  chloride,  reagent 54 

Peat,  analysis  of 60 

briquettes 59 

,  calorific  power 60 

,  formation 59 

,  moisture  in 5*9 

Petroleum,  crude,  analysis  of 68 

,  calorific  power 67 

,  formation  of 67 

Phosphorus,  reagent 54 

Potassium  hydrate,  reagent 54 

pyrogallate,  reagent 54 

"  Pounds  of  air  per  pound  of  coal " 28 

Producer-gas,  analysis  of 68 

,  calorific  power 69 

Pyrometer,  Le  Chatelier's  thermoelectric 26 

Quantity  of  heat  passing  up  chimney 29,  32 

Ratio  of  air  used  to  that  theoretically  necessary 32 

Sampling  apparatus 3,  6 

gases,  method  of 2 

,  tubes  for a 

solid  fuels,  method  of 69 

Semet-Solvay  coke-ovens 64 


INDEX  141 

PAGE 

Semi-bituminous  coal,  analysis  of 62 

Sodium  hydrate,  reagent 55 

pyrogallate,  reagent 55 

Specific  heat  of  various  gases 30 

Specifications  for  coal 115 

fuel  oil 1 26 

Spontaneous  combustion 66 

Storage  of  coal 66 

Sulphur,  boiling-point 26 

Sulphuric  acid,  fuming,  reagent 51 

Table  of  calorific  power  of  gases m 

liquids in 

solids 112 

melting-points  of  metals  and  salts 113 

metric  and  English  systems 114 

quantity  of  air  necessary  to  burn  gases no 

solubility  of  gases ; 113 

specific  gravity  of  gases 112 

tension  of  aqueous  vapor 109 

theoretical  quantity  of  air  supplied 114 

volumetric  specific  heats  of  gases 109 

weight  of  aqueous  vapor  in  air 109 

weights  of  gases 112 

Tanbark,  calorific  power  of 112 

Temperature,  measurement  of 25 

Thermometers 25 

,  testing  of 26 

Tubes  for  sampling 2 

Volatile  matter,  determination  of 70 

Water-gas,  analysis  of 69 

,  calorific  power 69 

\A  heat  straw,  calorific  power 112 

Wood,  analysis  of 59 

,  calorific  power 59 

,  moisture  in 58,  59 


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DANA — First  Appendix  to  Dana's  New  "  System  of  Mineralogy.".  Large  8vo,     1  00 

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JOHANNSEN — Determination  of  Rock-forming  Minerals  in  Thin  Sections,  8vo, 

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18 


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GOESEL — Minerals  and  Metals:  A  Reference  Book 16mo,  mor.,     3  00 

IHLSENG — Manual  of  Mining S^vo,     5  00 

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HANAUSEK — The  Microscopy  of  Technical  Products.      (WINTON.) 8vo,     5  00 

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WESTERMAIER — Compendium  of  General  Botany.      (SCHNEIDEP.) 8vo,     2  00 

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20 


UNIVERSITY  OF  CALIFORNIA  LIBRARY 
BERKELEY 


Return  to  desk  from  which  borrowed. 


below> 


JAN     4  1950 

APR  £0  1952 


'  |5 


DEC  29  1952 


LD  21-100m-9,'481B399sl6)476 


269001 


Engineering 
Library 


UNIVERSITY  OF  CAIylFORNIA  IJBRARY 


